Thermoelectric generation contributes to 80% of global electricity production. Cooling of thermoelectric plants is often achieved by water abstractions from the natural environment. In England and Wales, the electricity sector is responsible for approximately half of all water abstractions and 40% of non-tidal surface water abstractions. We present a model that quantifies current water use of the UK electricity sector and use it to test six decarbonisation pathways to 2050. The pathways consist of a variety of generation technologies, with associated cooling methods, water use factors and cooling water sources. We find that up to 2030, water use across the six pathways is fairly consistent and all achieve significant reductions in both carbon and water intensity, based upon a transition to closed loop and hybrid cooling systems. From 2030 to 2050 our results diverge. Pathways with high levels of carbon capture and storage result in freshwater consumption that exceeds current levels (37–107%), and a consumptive intensity that is 30–69% higher. Risks to the aquatic environment will be intensified if generation with carbon capture and storage is clustered. Pathways of high nuclear capacity result in tidal and coastal abstraction that exceed current levels by 148–399%. Whilst reducing freshwater abstractions, the marine environment will be impacted if a shortage of coastal sites leads to clustering of nuclear reactors and concentration of heated water discharges. The pathway with the highest level of renewables has both lowest abstraction and consumption of water. Freshwater consumption can also be minimised through use of hybrid cooling, which despite marginally higher costs and emissions, would reduce dependence on scarce water resources thus increase security of supply.