Abstract In the search for new advanced 2D materials for technological applications and to expand the research of non‐van der Waals (non‐vdW) 2D electronic devices, this study presents a novel strategy for liquid phase exfoliation (LPE) of non‐vdW Cr 2 S 3 to produce Cr 2 S 3 nanosheets (NSs). By utilizing N ‐methyl‐2‐pyrrolidone (NMP), bulk Cr 2 S 3 is separated along the (001) plane, resulting in the formation of NSs with an average thickness of ≈3 nm. Various characterization techniques are applied to the Cr 2 S 3 material before and after LPE. Subsequently, the obtained Cr 2 S 3 NSs are integrated into a photoelectrochemical (PEC)‐type photodetector (PD) to evaluate the photoelectric conversion efficiency under varying conditions. The findings indicate that the developed PD exhibits a distinct self‐powered photodetection capability with a photocurrent ( P ph ) of 39.5 nA cm −2 , a photoresponsivity ( R ph ) of 622 nA W −1 , and a detectivity ( D* ) of 0.5 × 10 7 Jones under 350 nm irradiation at 0 V. Moreover, the PD demonstrates rapid response time (0.06 s) and good long‐term stability (over 15 days), thus providing valuable insight for the advancement of non‐vdW Cr 2 S 3 ‐based optoelectronic devices.