Semiconductor/superconductor hybrids exhibit a range of phenomena that can be exploited for the study of novel physics and the development of new technologies. Understanding the origin of the energy spectrum of such hybrids is therefore a crucial goal. Here, we study Josephson junctions defined by shadow epitaxy on InAsSb/Al nanowires. The devices exhibit gate-tunable supercurrents at low temperatures and multiple Andreev reflections (MARs) at finite voltage bias. Under microwave irradiation, photon-assisted tunneling (PAT) of MARs produces characteristic oscillating sidebands at quantized energies, which depend on MAR order, n, in agreement with a recently suggested modification of the classical Tien-Gordon equation. The scaling of the quantized energy spacings with microwave frequency provides independent confirmation of the effective charge, ne, transferred by the nth-order tunneling process. The measurements suggest PAT as a powerful method for assigning the origin of low-energy spectral features in hybrid Josephson devices.