Severe peripheral nerve injuries are threatening the life quality of human beings. Current clinical treatments contain some limitations and therefore extensive research and efforts are geared towards tissue engineering approaches and development. The biophysical and biochemical characteristics of nanomaterials are highly focused on as critical elements in the design and fabrication of regenerative scaffolds. Recent studies indicate that the electrical properties and nanostructure of biomaterials can significantly affect the progress of nerve repair. More importantly, these studies also demonstrate the fact that electroactive nanomaterials have substantial implications for regulating the viability and fate of primary supporting cells in nerve regeneration. In this review, we summarize the current knowledge of electroconductive and piezoelectric nanomaterials. We exemplify typical cellular responses through cell-material interfaces, and the nanomaterial-induced microenvironment rebalance in terms of several key factors, immune responses, angiogenesis and oxidative stress. This work highlights the mechanism and application of electroactive nanomaterials to the development of regenerative scaffolds for peripheral nerve tissue engineering.