The carbon intensity of the electricity used to charge an electric vehicle (EV) is dependent on when in the day charging occurs. However, persuading EV owners to adopt incentives to charge during off-peak hours is challenging. Here we show that governments could exploit the ‘window of opportunity’ created when people purchase their first EV to promote time-of-use tariffs. Email recipients (n = 7,038 EV owners) were more likely to click-through to an information webpage when the email emphasized specific reductions in home-charging costs versus general bill savings. However, the ‘window of opportunity’ for maximizing potential adoption is short; email open rates declined from over 70% immediately after purchase to 40% for recipients owning their EV for over three months. These results demonstrate the potential of prompts to change behaviours for which opt-out enrolment (where enrolment is automatic unless people explicitly opt out) would be unethical or less effective.