AbstractQudit entanglement is an indispensable resource for quantum information processing since increasing dimensionality provides a pathway to higher capacity and increased noise resilience in quantum communications, and cluster-state quantum computations. In continuous-variable time–frequency entanglement, encoding multiple qubits per photon is only limited by the frequency correlation bandwidth and detection timing jitter. Here, we focus on the discrete-variable time–frequency entanglement in a biphoton frequency comb (BFC), generating by filtering the signal and idler outputs with a fiber Fabry–Pérot cavity with 45.32 GHz free-spectral range (FSR) and 1.56 GHz full-width-at-half-maximum (FWHM) from a continuous-wave (cw)-pumped type-II spontaneous parametric downconverter (SPDC). We generate a BFC whose time-binned/frequency-binned Hilbert space dimensionality is at least 324, based on the assumption of a pure state. Such BFC’s dimensionality doubles up to 648, after combining with its post-selected polarization entanglement, indicating a potential 6.28 bits/photon classical-information capacity. The BFC exhibits recurring Hong–Ou–Mandel (HOM) dips over 61 time bins with a maximum visibility of 98.4% without correction for accidental coincidences. In a post-selected measurement, it violates the Clauser–Horne–Shimony–Holt (CHSH) inequality for polarization entanglement by up to 18.5 standard deviations with an S-parameter of up to 2.771. It has Franson interference recurrences in 16 time bins with a maximum visibility of 96.1% without correction for accidental coincidences. From the zeroth- to the third-order Franson interference, we infer an entanglement of formation (E_of) up to 1.89 ± 0.03 ebits—where 2 ebits is the maximal entanglement for a 4 × 4 dimensional biphoton—as a lower bound on the 61 time-bin BFC’s high-dimensional entanglement. To further characterize time-binned/frequency-binned BFCs we obtain Schmidt mode decompositions of BFCs generated using cavities with 45.32, 15.15, and 5.03 GHz FSRs. These decompositions confirm the time–frequency scaling from Fourier-transform duality. Moreover, we present the theory of conjugate Franson interferometry—because it is characterized by the state’s joint-temporal intensity (JTI)—which can further help to distinguish between pure-state BFC and mixed state entangled frequency pairs, although the experimental implementation is challenging and not yet available. In summary, our BFC serves as a platform for high-dimensional quantum information processing and high-dimensional quantum key distribution (QKD).