Urban freight vehicles significantly impact the urban environment due mainly to traffic congestion, reduction in road capacity and pollutant emissions. Introducing low emission vehicles is one of the major measures foreseen in alleviating negative externalities. In this context, city logistics may represent a market niche for the deployment of electric vehicles. This paper introduces a methodology based on the Systems of Innovation approach to examine the process by which electric vehicles may be introduced in city logistics. The proposed methodology considers the complex interactions between actors and institutions and proposes a Systems' of Innovation Framework, which combines in a matrix the actors, the mechanisms and market conditions providing an instrument by which to qualitatively assess the current status and estimate future requirements and pre-conditions for innovation uptake. Applied to the case of electric vehicles in city logistics, the proposed framework is used to examine “who” should act, “how to act”, “what to act upon” and “when” to intervene. Findings indicate the need to transfer leadership from central authorities to municipal authorities in order to move from the initiation stage to the implementation stage. The importance of strong networks between innovation actors and respective building of capacities is considered of importance.