Zinc phosphide, Zn3P2, is a semiconductor with a high absorption coefficient in the spectral range relevant for single junction photovoltaic applications. It is made of elements abundant in the Earth's crust, opening up a pathway for large deployment of solar cell alternatives to the silicon market. Here we provide a thorough study of the optical properties of single crystalline Zn3P2 thin films grown on (100) InP by molecular beam epitaxy. The films are slightly phosphorus-rich as determined by Rutherford backscattering. We elucidate two main radiative recombination pathways: one transition at approximately 1.52 eV attributed to zone-center band-to-band electronic transitions; and a lower-energy transition observed at 1.3 eV to 1.4 eV attributed to a defect band or band tail related recombination mechanisms. We believe phosphorus interstitials are likely at the origin of this band.