Organic nonvolatile memory devices have garnered significant attention as next-generation electrical memory units owing to their potential for low-cost and straightforward fabrication through a solution process. In this study, we successfully fabricated fully solution-processed organic resistive random access memory (RRAM) devices using poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as the resistive switching (RS) layer, with poly(3,4-ethylene-dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) employed as the top electrode. Additionally, to enhance performance further, a polyethyleneimine (PEIE) interlayer was introduced between the bottom electrode and the P3HT:PCBM RS layer. The resulting organic RRAM devices with the PEIE interlayer exhibited bipolar resistive switching, with improved endurance increasing from 50 to 100 cycles, a retention time of 103 s, and a low SET voltage of 0.7 V. The organic RRAM devices featuring the PEIE interlayer demonstrated superior RS performance attributed to the higher Schottky barrier at the interface between the bottom electrode and the active switching layer, creating an asymmetric structure. I–V curve fitting confirmed that the potential switching mechanism involved Schottky emission in the high-resistance state and Ohmic conduction in the low-resistance state. Our findings suggest that organic RRAM devices with a PEIE interlayer hold promise for stable nonvolatile memory applications.