The present work aims at analyzing and comparing trigeneration systems (for the simultaneous production of electricity, heating and refrigeration) of different architectures based on energetic and exergetic efficiencies and on CO2 emissions. Trigeneration systems are regarded as more efficient in energy conversion, if compared to conventional systems, due to the recovery of waste heat from the heat engine. The waste heat is used for different purposes, including heating, chiller driving or electricity generation. Four trigeneration configurations (with vapor compression chiller, absorption chiller, with a combination of the two previous cycles, or combined with an organic Rankine cycle) were studied. Mathematical models resulting from the energy and exergy balances and from the calculation of CO2 emissions were developed taking into account that the three energy demands (electricity, heating and refrigeration) are independent from the trigeneration system performance. Solution of the resulting equations indicated an optimal point of operation, for all trigeneration architectures under study, where the waste heat recovered for heating equals the heating demand. At this point, the energy utilization factor (first Law indicator) and the exergy efficiency reach their maximum value, and the CO2 emissions, its lowest. Another important finding is that the configuration with best performance, from the energetic, exergetic, or environmental point of view, will depend on how the energy demands relate to each other.