The energy transition requires widespread electrification of the transport sector. To promote the penetration of electric vehicles (EVs), it is essential to understand consumers’ perceptions and behavior, particularly regarding the main determinants of EV purchase and the acceptance of electric mobility (EM). With this aim, we focused on an industrialized city in Portugal, addressing the differences between the effective ownership of an EV and the acceptability of EM and between the domestic sector (DS) and the business sector (BS) through questionnaires. Our results indicate that sociodemographic variables are the main determinants of the purchase of EVs and the acceptance of EM in the DS. Men and higher income individuals are more likely to own an EV. On the other hand, younger generations are more likely to have high EM acceptance. Individuals who already own an EV are the ones that have the desire and economic means to do so, regardless of any incentives. Still, widespread market penetration of EVs requires incentives for individuals who desire to own one of these vehicles but do not have the economic power to do so. Additionally, the DS and the BS behave differently; hence, specially designed policies are needed.