Abstract Polyethylenimine ethoxylated (PEIE) and polyethyl-enimine (PEI), the two kinds of interface buffer layer, are widely used in the organic light-emitting diodes and solar cells for band alignment adjustment. In this report, we carefully studied the influence of the inserting organic layer on the graphene nanowalls(GNWS)/Si junction quality and the photoresponse of the Schottky devices. We found that thinner layers of PEI could decrease the dark current and improve the photo-to-dark ratio to 105 for n-Si devices. The s-kink effect and degradation of open circuit voltage could be observed for thicker thickness and excessive doping. Relatively, PEIE with stable thin layer not only improve the rectifying characteristics of p-Si devices but also the incident photon conversion efficiency. The maximus IPCE could reach 44% and be adjusted to zero by the reverse bias. The tunneling inhibition for electrons can be alleviated by increasing the barrier height. Our results provide an attractive method to improve the efficiency of pristine GNWs/Si junction with interface doping and passivation.