This review describes the input of sol-gel chemistry to the immobilization of polyol dehydrogenases on electrodes, for applications in bioelectrocatalysis. The polyol dehydrogenases are described and their application for biosensing, biofuel cell and electrosynthesis are briefly discussed. The immobilization of proteins via sol-gel approaches is described, including a discussion on the difficulty to maintain the activity of proteins in a silica matrix and the strategies developed to offer a proper environment to the proteins by developing optimal organic-inorganic hybrid materials. Finally, the co-immobilization of the NAD(+) co-factor and of mediators for the elaboration of reagentless devices is presented, based on published and original data. All-in-all, sol-gel approaches appear to be a very promising for development of original electrochemical applications involving dehydrogenases in near future.