Organic memristive devices are gaining an increasing and considerable interest due to their attractive characteristics and potential applications, spanning from neuromorphic electronics to biosensing. In this work, a low-voltage operating memristive device was fabricated using a printed resistive switching (RS) layer consisting of poly (3,4-ethylene dioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) and poly(vinyl alcohol) (PVA). Scaling of the device dimensions (i.e., 5 and 3 μm channel length) proved to be a successful strategy to trigger the memristive behavior of the RS layer. Exposing the RS blend to high humidity, as well as to a fully aqueous electrolyte, enabled low-power (V = ± 1.0 V and I ≈ 1 μA) operation for the device, paving the way for the employment of organic memristive devices in future biosensing applications. On the basis of experimental conditions, the device exhibited either zero-crossing or non-zero-crossing current–voltage hysteresis, further emphasizing its versatile operational characteristics. The experimental findings were further supported by a theoretical model describing the memristive and memcapacitive behavior of the device.