Organizations in today’s supply chains strive for transportation activities optimization. However, transportation is a significant environmental impact activity. Particularly, road transportation is the highest emission rate source and the most widespread modality for last-mile delivery. In this context, the use of performance management tools, such as key performance indicators (KPIs), is a strategy to reach both economic-operative and environmental benefits. Among all KPIs, overall equipment effectiveness (OEE) is one of the most suitable KPIs to measure the utilization of an industrial asset. In the transportation sector, a variant of the OEE, known as the transportation overall vehicle effectiveness (TOVE), is used to define the performance of vehicle distribution activities, such as road transportation for last-mile delivery and urban logistics. Although TOVE is effective for evaluating vehicle performance in terms of administrative availability, operating availability, performance, and quality, the indicator does not take into the environmental impact related to road transportation activities. Literature has proposed several formulations to quantify transport carbon emissions, most of which are linear relationships to the distance travelled. However, these models are not suitable for assessing the TOVE performance of road transportation activities. This paper aims to compare the performance of last-mile delivery in terms of TOVE and carbon emissions evaluated with a distance travelled formulation in two different scenario systems. The comparison shows the inadequacy of TOVE in terms of environmental sustainability, as maximizing road transport performance while ignoring the environmental dimension excludes the minimization of CO2 emissions. Therefore, the foundation for future developments of TOVE for sustainable road transportation can be established from this divergence.