To achieve a sustainable electricity grid, affordable and dispatchable power capacity that supports grid stability and does not increase atmospheric CO2 levels will be required. Combined cycle gas turbines (CCGTs) with post-combustion CO2 capture (PCC) can meet these requirements by capturing and permanently storing all combustion CO2 emissions and, coupled with negative emissions technologies, any remaining life-cycle emissions. For the first time, we present a comprehensive analysis of the technical and financial challenges of producing zero-carbon electricity from CCGTs on a life-cycle basis. We conclude that when the design is optimised, fossil CO2 capture fractions can be increased from 96% to 100% with minimal process modification, commercially available technology and an additional 0.5% decrease in thermal efficiency. This represents a significant 60–70% reduction in the additional efficiency penalty required to reach zero CO2 emission operation. The Cost of CO2 Avoided of 100% fossil CO2 capture is just 128 £/tCO2, a 3 £/tCO2 increase over the 95% gross CO2 capture fraction required to permit PCC projects in the UK. Indeed, within the bounds of the UK power CCS business model, we show that 100% fossil CO2 capture maximises both variable and capacity payments to the producer, resulting in a 2% decrease in the cost of power produced. For zero-carbon electricity on a life-cycle basis, the recapture and permanent geological storage of all remaining life-cycle CO2e emissions from plant construction & decommissioning, CO2 T&S network operation and the natural gas supply chain (operational CO2e emissions and methane leakage) increases the median Cost of CO2 Avoided to 178 £/tCO2 (130–371 £/tCO2), leading to the novel conclusion that a market mechanism equating to a CO2 price of over 178£/tCO2 is likely sufficient to incentivise the development of truly CO2-neutral CCGTs. Display omitted •The CCA & LCOE for 100% fossil CO2 capture is estimated at 128£/tCO2 & 104 £/MWhe•Permanent scope 2 and 3 emission recapture adds 10–114£/MWhth to electricity costs.•The recapture of 8.6–11.8 MtCO2 of CO2 over the plant lifetime is required.•Electricity output penalty, capital and operational costs increase by 8, 4 and 2.3%.•CCS business models in the UK support 100% fossil CO2 capture.