Concerns about Peak Oil, political instability in the Middle East, health hazards, and greenhouse gas emissions of fossil fuels have stimulated interests in alternative fuels such as biofuels, natural gas, electricity, and hydrogen. Alternative fuels are expected to play an important role in a transition to a sustainable transportation system. One of the major barriers to the success of alternative-fuel vehicles (AFV) is the lack of infrastructure for producing, distributing, and delivering alternative fuels. Efficient methods that locate alternative-fuel refueling stations are essential in accelerating the advent of a new energy economy. The objectives of this research are to develop a location model and a Spatial Decision Support System (SDSS) that aims to support the decision of developing initial alternative-fuel stations. The main focus of this research is the development of a location model for siting alt-fuel refueling stations considering not only the limited driving range of AFVs but also the necessary deviations that drivers are likely to make from their shortest paths in order to refuel their AFVs when the refueling station network is sparse. To add reality and applicability of the model, the research is extended to include the development of efficient heuristic algorithms, the development of a method to incorporate AFV demand estimates into OD flow volumes, and the development of a prototype SDSS. The model and methods are tested on real-world road network data from state of Florida. The Deviation-Flow Refueling Location Model (DFRLM) locates facilities to maximize the total flows refueled on deviation paths. The flow volume is assumed to be decreasing as the deviation increases. Test results indicate that the specification of the maximum allowable deviation and specific deviation penalty functional form do have a measurable effect on the optimal locations of facilities and objective function values as well. The heuristics (greedy-adding and greedy-adding with substitution) developed here have been identified efficient in solving the DFRLM while AFV demand has a minor effect on the optimal facility locations. The prototype SDSS identifies strategic station locations by providing flexibility in combining various AFV demand scenarios. This research contributes to the literature by enhancing flow-based location models for locating alternative-fuel stations in four dimensions: (1) drivers' deviations from their shortest paths, (2) efficient solution approaches for the deviation problem, (3) incorporation of geographically uneven alt-fuel vehicle demand estimates into path-based origin-destination flow data, and (4) integration into an SDSS to help decision makers by providing solutions and insights into developing alt-fuel stations.