Multi-walled carbon nanotube (MWCNT)/poly(vinyl alcohol) (PVA) nanocomposite hydrogels were prepared by freezingthawing method for the electro-responsive transdermal drug delivery. MWCNTs were used as the functional ingredient to improve both mechanical and electrical properties of MWCNT/PVA nanocomposite hydrogels. The morphology of nanocomposites revealed the uniform distribution of MWCNTs and the good interfacial contact. The compression moduli of hydrogel matrices increased greatly from 40 to 1500 kPa by forming MWCNT/PVA nanocomposites. The swelling ratio of MWCNT/PVA nanocomposites decreased as the content of MWCNTs increased under no electric voltage applied. However, the swelling ratio of MWCNT/PVA nanocomposites increased as the content of MWCNTs increased under electric voltage applied and the applied electric voltage increased. The drug was released in the electro-responsive manner through the skin due to the electro-sensitive swelling characteristics of MWCNT/PVA nanocomposite hydrogels.