<p>Photonic time crystals host a variety of intriguing phenomena, from wave amplification and mixing to exotic band structures, all stemming from the time-periodic modulation of optical properties. While these features have been well described classically, their quantum manifestation when coupled to an atomic electric dipole has remained elusive. Here, we introduce a quantum electrodynamical model of photonic time crystals that reveals a deeper connection between classical and quantum pictures: the classical momentum gap arises from a localization-delocalization quantum phase transition in a Floquet-photonic synthetic lattice. Leveraging an effective Hamiltonian perspective, we pinpoint the critical momenta and highlight how classical exponential field growth manifests itself as wave-packet acceleration in the quantum synthetic space. Remarkably, when a two-level atom is embedded in such a photonic time crystal, its Rabi oscillations undergo irreversible decay to a half-and-half mixed state—a previously unobserved phenomenon driven by photonic delocalization within the momentum gap, even with just a single frequency mode. Our findings establish photonic time crystals as versatile platforms for studying nonequilibrium quantum photonics and suggest new avenues for controlling light matter interactions through time domain engineering.</p>