In view of impending depletion of hydrocarbon fuel resources and their negative environmental impact, it is imperative to significantly increase the energy conversion efficiency of hydrocarbon-based power generation systems. The combination of a hydrocarbon decomposition reactor with a direct carbon and hydrogen fuel cells (FC) as a means for a significant increase in chemical-to-electrical energy conversion efficiency is discussed in this paper. The data on development and operation of a thermocatalytic hydrocarbon decomposition reactor and its coupling with a proton exchange membrane FC are presented. The analysis of the integrated power generating system including a hydrocarbon decomposition reactor, direct carbon and hydrogen FC using natural gas and propane as fuels is conducted. It was estimated that overall chemical-to-electrical energy conversion efficiency of the integrated system varied in the range of 49.4-82.5%, depending on the type of fuel and FC used, and CO2 emission per kW(el)h produced is less than half of that from conventional power generation sources. (C) 2009 Elsevier B.V. All rights reserved.