By conducting a cross-sectional survey at Deutsche Post, a major German postal delivery service provider, we examine to what extent commercial drivers accept the substitution of conventional cars with light-duty e-vehicles (LDEVs). Specifically, we explore drivers’ acceptance from two perspectives. First, we investigate drivers’ perceived satisfaction with LDEVs compared to conventional vehicles. Second, we question whether electric cars in general increase drivers’ perceived efficiency of them. Combining these two perspectives, we show that the greater the drivers’ overall perceived satisfaction with LDEVs is, the higher is the drivers’ perceived efficiency of LDEVs. We prove this by means of perceived usefulness (perceived relative advantage) and perceived ease of use (the opposite of perceived complexity) of LDEVs, using adaptations of Davis’ Technology Acceptance Model and Rogers’ Diffusion of Innovations Theory to form our Unified Technology Acceptance Model (UTAM). Our findings suggest that, on average, drivers are slightly more satisfied with the LDEVs than with the available conventional cars (n = 66). If drivers were able to choose their preferred vehicles, the majority of them would favor LDEVs. We detect statistically significant patterns of latent measures affecting perceived usefulness and perceived ease of use of LDEVs. Although this paper focuses on German delivery service employees, the methodology presented here could easily be applied to any other enterprise in the growing logistics segment which plans to electrify its car fleet. Hence, our contributions are valuable for transportation research and, more specifically, to all potential commercial EV drivers, e.g., our insights might be relevant for the approx. 500,400 drivers employed in the German logistics sector alone.