The synthesis of a vanadium dioxide (VO 2 ) film using atomic layer deposition (ALD) with vanadium tetrachloride (VCl 4 ) as a precursor for the realization of programmable memory devices is reported. X-ray diffraction analysis revealed the epitaxial growth of VO 2 on c-Al 2 O 3 . The phase transition was monitored using resistivity measurements across varying temperatures, demonstrating a decrease of >4 orders of magnitude at the transition temperature, thereby confirming the high quality of the material. From this material, memristive devices are fabricated as resistive random-access memory (RRAM). On the basis of spiking voltage inputs, these RRAM exhibited cycle stability over 512 cycles and state retention stability for >450 s, showing <2% drift. With respect to synaptic-like applications, the RRAM devices were piloted through step patterns to enable multilevel memory states. These ALD-grown VO 2 -based devices demonstrate potential for use as synaptic connections with multiweight synapses, advancing scalability in neuromorphic applications.