Interfacial modification between the electrode and the overlying organic layer has significant effects on the charge injection and collection and thus the device performance of organic photodetectors. Here, we used copper(I) thiocyanate (CuSCN) as the anode interfacial layer for organic photodetector, which was inserted between the anode and an organic light-sensitive layer. The CuSCN layer processed with ethyl sulfide solution presented similar optical properties to the extensively used anode interlayer of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), while the relatively shallow conduction band of CuSCN resulted in a much higher electron-injection barrier from the anode and shunt resistance than those of PEDOT:PSS. Moreover, the CuSCN-based device also exhibited an increased depletion width for the PEDOT:PSS-based device, as indicated by the Mott-Schottky analysis. These features lead to the dramatically reduced dark current density of 2.7 × 10-10 A cm-2 and an impressively high specific detectivity of 4.4 × 1013 cm Hz1/2 W-1 under -0.1 V bias and a working wavelength of 870 nm. These findings demonstrated the great potential of using CuSCN as an anode interfacial layer for developing high-performance near-infrared organic photodetectors.