A plethora of decarbonization pathways have been suggested over the last few years and it has been generally accepted that substantial progress toward more sustainable transport requires a significant contribution from the freight sector. Deep decarbonization of road freight by conventional means is difficult, so alternatives need to be investigated. One of the most potentially beneficial approaches is electrification which is the subject of the paper. The challenges of conventional electric freight vehicles for long-haul operations are discussed and then innovative power delivery systems that could alleviate the problems are reviewed. A logistics concept to provide a framework for the electrification of most road freight transport operations is considered and based on that, simulation tools and methods are presented to set the performance requirements for a practical system. Finally, four case studies are developed for assessing the feasibility of electrification of various road freight operations. Overall, it is shown that electrification of road freight is a viable route for more sustainable transportation.