In this study, the electrical properties of an Al/p-Si metal/semiconductor photodiodes with Tetracyanoquinodimethane–Polyvinyl chloride (TCNQ–PVC) and PVC–TCNQ:ZnO interfacial layers were investigated. Growing of the interfacial layers on p-Si were fulfilled using electrospinning method as a fiber form. Al metallic and ohmic contacts were deposited via physical vapor deposition method. Scanning electron microscopy (SEM) pictures of the devices were captured to examine the morphology of the structure. Within the scope of electrical characterization, I–V measurements of the Al/PVC–TCNQ/p-Si and Al/PVC–TCNQ:ZnO/p-Si devices were accomplished both in the dark and under illumination conditions. Various device parameters, such as ideality factor and barrier height values were determined from I–V characteristics. Although the ideality factor values were obtained as 8.47 and 6.85 for undoped and ZnO-doped Al/PVC–TCNQ/p-Si diodes, the barrier height values were calculated as 0.84 for both devices. When a comparison was made between ZnO doped and undoped Al/PVC–TCNQ/p-Si diodes, it was evaluated that the rectification and photoresponse properties of the heterojunction diode was improved with ZnO dopant.