The entry of various plug-in electric vehicles (PEVs) into the passenger vehicle sector provides novel opportunities to learn about the potential for future PEV markets. However, early PEV buyers (or “Pioneers”) can substantially differ from present conventional vehicle owners that have interest in purchasing PEVs in the future (or the “Potential Early Mainstream buyers”). To compare the characteristics, preferences, and motivations of Pioneers and Potential Early Mainstream buyers, we draw data from the Canadian Plug-in Electric Vehicle Study, a three-part mixed-mode survey with samples of PEV owners (n = 94) and conventional new vehicle buyers (n = 1754). We identify several significant differences in household characteristics, including income, education, and recharge access. In terms of preferences, Pioneers express extremely high valuation of PEVs and prefer pure battery electric vehicle (BEV) designs over plug-in hybrid electric (PHEV) designs. In contrast, Potential Early Mainstream respondents prefer PHEVs. Both Pioneer and Potential Early Mainstream respondents are similarly cautious about controlled charging programs, but Pioneers place five times as much value on using electricity generated from renewable sources than the Potential Early Mainstream. Pioneers also tend to have different motivations, including significantly higher levels of environmental concern, and higher engagement in environment- and technology-oriented lifestyles. Policymakers, automakers, and electric utilities that anticipate a transition to electric mobility ought to consider how potential future PEV buyers may differ in their vehicle preferences, usage and motivations relative to current PEV owners.