Bio-energy with carbon capture and storage (BECCS) is an important greenhouse gas removal (GGR) technology with the potential to provide significant reductions in atmospheric CO2 concentration. The power generation efficiency of BECCS can be improved by using heat recovered from flue gas to supply energy requirements of the solvent regeneration process. This paper assesses the influence of solvent selection and biomass co-firing proportion on recoverable heat, energy efficiency and carbon intensity of a 500 MW pulverized fuel BECCS system. The effects of (i) coal type (high and medium sulphur content), (ii) biomass type (wheat straw and clean wood chips, (iii) variable moisture content, and (iv) biomass co-firing % on AFT and emissions of SOX and NOX was evaluated. Compared to firing of coal alone, co-firing low moisture biomass generated higher adiabatic flame temperature. As biomass co-firing proportion increased, SOX emissions decreased, whereas NOX emissions increased with greater AFT. Factors that enhanced BECCS efficiency included the use of high performance solvents and higher heat recovery (higher AFT and flue gas flow rate). These results lead to the development of a performance matrix which summarizes the effect of key process parameters.