Deep decarbonisation of road transportation is challenging. One of the most potentially beneficial approaches is electrification which is the subject of this PhD thesis. A widespread penetration of electric vehicles (EVs) across a large proportion of road transport demand is needed to realise the benefits of an electrified transport sector. However, this is dependent on overcoming significant barriers. This study performs a systematic analysis of how proven power charging technologies could be used to unlock the barriers to widespread electrification of road transportation. Various road transport sectors and type of journeys are explored including aspects of autonomous operations and novel wireless power transfer technologies. For each operation, a framework is proposed that allows the exploitation of current and potential future electrification technologies to enable shifting towards EVs. Based on that, simulation tools and methods are developed to calculate the power requirements of EVs and determine a suitable charging infrastructure. The additional power demand, electric load and the implications for the electricity supply network are explored. The total expenditure needed and the CO2 emission savings are also calculated for each investigated operation. Transitional strategies include the electrification of bus routes, refuse collection functions, home deliveries and aspects of autonomous operations for public transportation within the boundaries of the cities. In the long-term, focus is given on passenger cars and freight vehicles for both urban and inter-urban journeys. A nationwide adoption of all electrification strategies proposed in this thesis would increase the peak power demand of Great Britain by approximately 38 GW (72% of the current peak) and the electricity consumption by 180 TWh per year (45% of current consumption). The total capital cost required is calculated at £225 billion which is similar to the cost of other large infrastructure projects of the country. The impact would be a significant aggregate saving of approximately 2,000 MtCO2 between the numbers calculated for today's norms (2018) and those calculated for 2050.