Memristive devices have drawn considerable research attention due to their potential applications in non‐volatile memory and neuromorphic computing. The combination of resistive switching devices with light‐responsive materials is considered a novel way to integrate optical information with electrical circuitry. On the other hand, 2D materials have attracted substantial consideration, thanks to their unique crystal structure, as reflected in their chemical and physical properties. Although not the major focus, van der Waals solids are proven to be potential candidates in memristive devices. In this scheme, the majority of the resistive switching devices are implemented on planar flakes, obtained by mechanical exfoliation. Here a facile and robust methodology is utilized to grow large‐scale vertically aligned MoS2 (VA‐MoS2) films on standard silicon substrates. Memristive devices with the structure silver/VA‐MoS2/Si are shown to have low set‐ON voltages (<0.5 V), large‐retention times (>2 × 104 s), and high thermal stability (up to 350 °C). The proposed memristive device also exhibits long term potentiation/depression (LTP/LTD) and photo‐active memory states. The large‐scale fabrication, together with the low operating voltages, high thermal stability, light‐responsive behavior, and LTP/LTD, make this approach very appealing for real‐life non‐volatile memory applications.