This paper presents a detailed life-cycle assessment of the greenhouse gas emissions, cumulative demand for total and non-renewable primary energy, and energy return on investment (EROI) for the domestic electricity grid mix in the U.S. state of California, using hourly historical data for 2018, and future projections of increased solar photovoltaic (PV) installed capacity with lithium-ion battery energy storage, so as to achieve 80% net renewable electricity generation in 2030, while ensuring the hourly matching of the supply and demand profiles at all times. Specifically—in line with California’s plans that aim to increase the renewable energy share into the electric grid—in this study, PV installed capacity is assumed to reach 43.7 GW in 2030, resulting of 52% of the 2030 domestic electricity generation. In the modelled 2030 scenario, single-cycle gas turbines and nuclear plants are completely phased out, while combined-cycle gas turbine output is reduced by 30% compared to 2018. Results indicate that 25% of renewable electricity ends up being routed into storage, while 2.8% is curtailed. Results also show that such energy transition strategy would be effective at curbing California’s domestic electricity grid mix carbon emissions by 50%, and reducing demand for non-renewable primary energy by 66%, while also achieving a 10% increase in overall EROI (in terms of electricity output per unit of investment).