Quantum interference gives rise to the asymmetric Fano resonance line shape when the final states of an electronic transition follows within a continuum of states and a discrete state, which has significant applications in optical switching and sensing. The resonant optical phenomena associated with Fano resonance have been observed by absorption spectra, Raman spectra, transmission spectra, etc., but have rarely been reported in photoluminescence (PL) spectroscopy. In this work, we performed spectroscopic studies on layered chromium thiophosphate (CrPS4), a promising ternary antiferromagnetic semiconductor with PL in near-infrared wavelength region and observed Fano resonance when CrPS4 experiences phase transition into the antiferromagnetic state below Neel temperature (38 K). The photoluminescence of the continuum states results from the d band transitions localized at Cr3+ ions, while the discrete state reaches saturation at high excitation power and can be enhanced by the external magnetic field, suggesting it is formed by an impurity level from extra atomic phosphorus. Our findings provide insights into the electronic transitions of CrPS4 and their connection to its intrinsic magnetic properties.