Resistive switchable memory devices were fabricated using self-assembled composite thin films of asymmetric poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) block copolymers (BCP) and fullerene derivatives (PCBM). L1 (with a longer PS block) was comprised of discrete vertical P4VP nanocylinders embedded within the PS matrix whereas L2 (with a longer P4VP block) revealed a reverse morphology with a horizontal orientation. They were used to control the spatial location or distribution of the PCBM and the resultant memory characteristics. The devices with ITO/BCP:PCBM/Al configurations exhibited variable multi-electronic characteristics, changing from insulating to bistable memory switching and highly conducting, as the PCBM content increased. The L1:PCBM memory device showed non-volatile write-once-read-many-times (WORM) memory behavior but the L2:PCBM device exhibited a volatile nature of static random access memory (SRAM). Both L1 and L2:PCBM composite devices revealed the improved switching performance upon solvent annealing procedures of the composite thin film. Our results suggested that the controlled morphology of the BCP/PCBM composite could create nanoscale charge-storage elements for a high density memory device with a reduced bit cell size.