Focusing on the traditional principle of physical energy utilization, new integration concepts for combined cooling, heating and power (CCHP) system were identified, and corresponding systems were investigated. Furthermore, the principle of cascade utilization of both chemical and physical energy in energy systems with the integration of chemical processes and thermal cycles was introduced, along with a general equation describing the interrelationship among energy levels of substance, Gibbs free energy of chemical reaction and physical energy. On the basis of this principle, a polygeneration system for power and liquid fuel (methanol) production has been presented and investigated. This system innovatively integrates a fresh gas preparation subsystem without composition adjustment process (NA) and a methanol synthesis subsystem with partial-recycle scheme (PR). Meanwhile, a multi-functional energy system (MES) that consumes coal and natural gas as fuels simultaneously, and co-generates methanol and power, has been presented. In the MES, coal and natural gas are utilized synthetically based on the method of dual-fuel reforming, which integrates methane/steam reforming and coal combustion. Compared with conventional energy systems that do not consider cascade utilization of chemical energy, both of these systems provide superior performance, whose energy saving ratio can be as high as 10% 15%. With special attention paid to chemical energy utilization, the integration features of these two systems have been revealed, and the important role that the principle of cascade utilization of both chemical and physical energy plays in system integration has been identified.