This paper presents an evaluation of the environmental performance of an advanced zero emission plant (AZEP) including CO2 capture. The evaluation is conducted with the aid of an advanced exergoenvironmental analysis. The results are compared with those of a reference combined-cycle power plant without CO2 capture. Advanced exergy-based methods are used to (a) quantify the potential for improving individual components or overall systems, and (b) reveal detailed interactions among components—two features not present in conventional analyses, but very useful, particularly when evaluating complex systems. In an advanced exergoenvironmental analysis, the environmental impacts calculated in a conventional exergoenvironmental analysis are split into avoidable/unavoidable (to evaluate the potential for component improvement) and endogenous/exogenous (to understand the interactions among components) parts. As in the reference plant, the potential for reducing the environmental impact of the AZEP has been found to be limited by the relatively low avoidable environmental impact associated with the thermodynamic inefficiencies of several of its components. However, although the environmental impacts for the majority of the components of the plant are related mainly to internal inefficiencies and component interactions are of secondary importance, there are strong interactions between the reactor and some other components.