We use metal-assist chemical etching (MCE) method to fabricate nanostructured black silicon on the surface of C-Si. In our MCE process, a chemical reduction reaction of silver cation (Ag+) will happen on the surface of silicon substrate, and at the same time the silicon atoms around Ag particles are oxidized and dissolved, generating nanopores and finally forming a layer called black silicon on the top of the substrates. The nanopores have diameter and depth of about 400 nm and 2 μm, respectively. Furthermore, these modified surfaces show higher light absorptance in near-infrared range (800 to 2500 nm) compared to that of C-Si with polished surfaces, and the maximum light absorptance increases significantly up to 95% in the wavelength region of 400 to 2500 nm. The Si-PIN photoelectronic detector based on this type of black silicon, in which the black silicon layer is directly set as the photosensitive surface, has a substantial increase in responsivity with about 80 nm red shift of peak responsivity, particularly at near-infrared wavelengths, rising to 0.57 A/W at 1060 nm and 0.37 A/W at 1100 nm, respectively. Our recent novel results clearly indicate that nanostructured black silicon made by MCE has a potential application in near-infrared photoelectronic detectors.