Full chain energy performance is applied to a hybrid combined cooling, heating and power (CCHP) system running with methanol and solar energy. Results show that the overall energy efficiencies of six different cases range from 40% to 50% in summer condition, and 38% to 47% in winter condition. Combined with the traditional methanol production process, the CCHP systems are not energy efficient compared to the traditional energy supply systems from a full chain viewpoint no matter whether the solar energy is utilized. While combined with a polygeneration (PG) or polygeneration with CO2 capture (PG + CC) process, the CCHP system could achieve obvious improvements in overall energy efficiency due to the benefits from cogeneration and solar energy utilization, and thus could yield a high fossil energy saving ratio in comparison with the traditional energy supply system. The findings presented in this paper indicate that the complementation utilization of solar energy and fossil fuels through thermochemistry reactions is energy efficient and could be one of the potential options to utilize solar energy. (C) 2012 Elsevier Ltd. All rights reserved.