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The last mile of parcel deliveries is a key process to service providers, with global costs that reach up to 70 billion euros per year. Moreover, due to urban population growth and to the rise of e-commerce, the importance of last-mile deliveries and its impacts to the environment and quality of life in cities tend to increase even more. This chapter proposes a more comprehensive methodology to assess alternative last-mile distribution strategies in terms of environmental and economic aspects and presents an application to the distribution of a postal company located in the city of Rio de Janeiro, Brazil. We evaluated the use of small electric vehicles (i.e., tricycles) in the last mile deliveries by assessing two scenarios: (1) the baseline scenario using a light commercial vehicle and (2) a scenario using electric tricycles. Results indicated that the use of electric tricycle is a more feasible alternative regarding the economic and environmental aspects as well as to maintain the service level of the company.