This study analyzes the preference structure of buyer groups that influences their willingness to select CO2-saving power train technologies for medium-duty and heavy-duty vehicles (HDV). Based on the Technology–Organization–Environment framework for organizational adoption decision making and organizational buying criteria a theoretical construct was developed. Variables were validated in exploratory preliminary research and subsequently tested based on factor analysis using 27 survey items in a quantitative web-based study among 177 organizations operating HDV in Germany. Knowledge, experience, use and purchase consideration concerning alternative power train technologies and further measures to reduce fuel consumption were additionally queried. Based on a multiple linear regression analysis, key findings show that at the current stage of market maturity environmental attitude and corporate social responsibility exert the strongest significant influence on willingness to select CO2-saving power train technologies. A hierarchical cluster analysis revealed six customer groups in order to yield behavioral market segmentation. Hereby it is shown that the performed transportation tasks do not determine the preference structures. Early adopting organizations are larger than average and driven by non-economic aspects as image or corporate social responsibility, whereas the mass market awaits lower purchasing prices. Crossing this chasm will be a major challenge for policymaker and manufacturers.