We report the preparation of cadmium sulfide (CdS) and lead sulfide (PdS) nanoparticle-blended poly(vinylacetate) (PVA) composite nanofibers by using an electrospinning technique. The resultant nanofibers were observed to be very smooth with uniform diameters ranging from 100 to 400nm. The detailed analyses such as surface morphology, structure, bonding configuration, thermal, optical and electrical properties of the electrospun composite nanofibers were characterized. The introduced CdS and PdS nanoparticles in PVA were significantly enhanced by the electrical property of the composite nanofibers. The electrical conduction mechanism was further evaluated by studying the Fowler–Nordheim plots. Overall, the feasibility of obtaining uniformly dispersed CdS and PdS nanoparticles in PVA nanofibers can be useful for the realization of various nanotechnological device applications.