High-dimensional entanglement in qudit states provides a route to realize large-scale, precisely controllable, practical systems for advanced quantum information processing, quantum secured communications, quantum metrology, and complex quantum computation. Many quantum platforms are currently subject to extensive research for superdense encoding, such as trapped ions, superconducting circuits, defect centers in solid-state crystals, mechanical oscillators, and photons. While all platforms provide unique advantages as well as challenges, optical quantum states are of particular interest, because they can interact with other quantum systems, and can be transmitted over long distances while preserving their quantum coherence. A large variety of quantum resources using optical quantum states has been demonstrated, however most of implementations suffer from high complexity, ultimately limiting their scalability. Mode-locked biphoton frequency combs (BFCs), which are intrinsically multimode in the temporal and frequency degrees of freedom within a single spatial mode, naturally facilitating the generation and manipulation of high-dimensional entanglement in large-scale quantum systems. Such BFCs have been demonstrated over fiber- and chip-compatible platforms. However, there is a huge gap between the maximal number of time and frequency modes and the dimensionality of the entanglement characterized experimentally, with the major challenge of certifying such high-dimensional entanglement by a number of accessible measurements. Quantifying and certifying the amount of entanglement in a high-dimensional quantum system has been a long-standing question in the quantum optics community. Therefore, there is an urgent need to generate and to certify large and complex photon states without increasing source complexity, while still enabling coherent quantum state control and detection. In this dissertation, we focus on realization, quantification and applications of such high-dimensional optical quantum states. First, we demonstrated a high-dimensional doubly-resonant BFC by achieving record-high Hong-Ou-Mandel (HOM)-interference revivals and Franson interference recurrences. We certify a Hilbert-space high-dimensionality of at least 648 using a time-bin Schmidt number of 18 and frequency-polarization hyperentanglement in such a BFC. Second, we demonstrated first high-dimensional entanglement distribution using a singly-resonant BFC with the record-high Franson visibility 98.81% with 16 time-bins and average frequency-binned Franson visibility of 98.03% for 5 frequency-pairs at a 10-km distance. High-dimensional time-frequency entanglement is certified by frequency-bin Schmidt number of 4.17 and a measured time-bin Schmidt number of 13.13. Third, we explore the role of cavity finesse within our singly-resonant BFCs. Increasing cavity finesse can increase the probability to detect single-photons at multiple cavity round-trips and can flatten the fall-off of Franson recurrence visibilities. Fourth, we demonstrate first genuine time-reversible ultranarrow photon-pair source with over 5,000 modes using asymmetric singly-resonant BFCs operating in telecom-band. Fifth, we demonstrate essential functionalities for quantum networking, including frequency-multiplexed high-dimensional time-bin encoding with our BFC sources. We perform proof-of-principle frequency-multiplexed high-dimensional time-bin (QKD) using a singly-resonant BFC. We measured photon information efficiency (PIE) up to 15 bits per coincidence for 5 frequency pairs of a singly-resonant BFC and 5 kbits/s raw key rate towards high-dimensional quantum communication. The secure key rate (SKR) is obtained to be 1.1 kbits/s with PIE of 2.41 bits per coincidence, secured by our high-visibility frequency-binned Franson interference. Finally, we investigated the first experimental demonstration of chip-scale two-qubit SWAP gate that can be used for scalable high-dimensional quantum computing. We observe high fidelity in the SWAP gate logical basis, and phase coherent quantum fringes after SWAP operation with high visibility. We have investigated the fundamental physics of BFC on scaling its Hilbert space dimensionality for complex quantum information processing, the versability of singly-resonant BFC for real-world quantum photon efficient communications, and the silicon photonic two-qubit SWAP gate operation towards high-dimensional quantum optical computations. Our work represents an important step forward in the generation, certification and distribution of complex quantum states using telecom compatible fiber systems in a single spatial mode. Such large-scale quantum states would then be well suited for the applications, including high-dimensional entanglement teleportation, quantum simulations, interconnecting matter qubits, on-chip quantum computing and storage, and various quantum communication protocols based on superdense time- and frequency-bin encodings.