Crystals of layered semiconductor are grown by Bridgman technique and are studied them under twophoton excitation by a Q-switched 20-ns pulse laser. The photoluminescence (PL) emission spectra of the crystals are measured at various pumping powers and temperatures. The PL spectra appear broad and structureless emissions with their peaks in the green spectral region. The characteristic emissions are fromself-trapped excitons of the crystals. An analysis of the spectra measured at various pumping powers shows a quadratic dependence of the PL peak intensity on the power, confirming a biphotonic process of the two-photonpumping. The temperature dependence shows an enhancement of the nonlinear response at low temperatures. The activation energy is estimated and found to be 2.4 meV. The roles of the bound excitons in the observed PL are discussed briefly.