For the purpose of paving the way for reducing environmental pollution globally, adapting green energy to people’s lives in more areas is seen as a good solution. The strategic plan implemented to prevent possible energy and water shortages in the future includes cleaning the environment and air from carbon emissions as soon as possible. Countries are taking mandatory sectoral and individual measures to remove the use of CO2-based fuels. As a part of the sustainable development process for Turkey, which is trying to convince its individuals to use more green energy, it is important for society to adopt more electric vehicles. However, there are few internationally accepted studies on the adoption of EVs in Turkey, and a limited number of studies include individuals’ environmental concerns (EC) and green trust (GT) structures. In this research, which we started on the basis of filling this literature gap by taking behavioral factors into account, we expand the TPB framework (subjective norm (SN), attitude (AT), and perceived behavioral control (PBC)) with the “EC” and “GT” constructs. So, with this research, we examine the behavioral factors that affect the intention to purchase electric vehicles (EVPI) of consumers residing in Turkey, based on the theory of planned behavior. Thus, we aim to reveal the barriers to the adoption of EVs in Turkey with an empirical application and SEM analysis. The first phase includes a review of the literature, adaptation of the survey, and development of the hypotheses. The second phase involves conducting a survey with 626 consumers whose information was obtained from four dealers in Turkey. We used Cronbach’s alpha and CFA analyses on the data obtained from the survey. In the final phase, we performed an SEM analysis for our extended theory of planned behavior (ETPB) and hypotheses. The CFA results revealed that the survey showed compatibility with EV purchase intentions. The SEM results indicated that the behavioral constructs of AT, PBC, EC, and GT were positively correlated with EV purchase intentions, and our new ETPB model, extended with EC and GT, was suitable for predicting consumers’ EVPI, suggesting that EVPI are a result of behavioral constructs. This study is unique for being the first in Turkey to focus on whether the factors of EC or GT can predict consumers’ EVPI. On the other hand, it was found that SN had a negative effect on consumers’ EVPI, and this result was in agreement with some studies in the literature and contradicted by others. In addition, we make suggestions based on the findings of the research to the country and related sector managers in order for the country to progress at a level that will set an example for other developing countries in its sustainable development plan. This study contributes to the EVs industry by revealing the consumers’ responses and increasing their marketing efforts. Our findings constitute a comprehensive example for further research on sustainable consumption, EVs, EVPI, and ETPB.