The photoluminescence of oriented thin-film CdS on glass formed by laser deposition was investigated employing 200 fs, 1.54 eV laser pulses at room temperature. The ultrafast excitation caused a two-photon absorption process, which results in purely green emission at the band gap. The spectra are fitted very well by the application of the van Roosbroeck–Shockley relation, density of states, and Urbach’s rule demonstrating the intrinsic character of the radiative recombination. It is further shown that the energy position of the emission peak depends on the polarization of the impinging laser beam due to the dichroism of the highly oriented films.