Structural and electrochemical characteristics of hypo-hyper d-electrocatalytic materials aimed for preparation of electrodes for hydrogen evolution were Studied and modified in order to improve their performances. All studied materials were of general composition 10% Ni + 18% TiO2 + C. All materials were prepared of amorphous or crystalline TiO2, crystalline Ni or NiCo (10-20 nm) and Vulcan XC-72, by sol-gel procedure. Both, material's intrinsic catalytic activity and surface area were affected by applied modifications. As a result, the electrocatalytic activity was improved, e.g. transformation of TiO2 into anatase form lowers the HER overpotential for 60 mV. Introduction of MWCNTs was even more effective, lowering eta for 120 mV. Co addition to metallic phase lowers 17 for utmost 195 mV. Combined modification of TiO2 and carbon substrate lowers eta for 145 mV, while the complete modification of all three catalyst's components was the most effective with 230 mV decrease of overpotential. (c) 2006 Elsevier Ltd. All rights reserved.