A value chain is a series of events that takes a raw material and with each step adds value to it. Global interest in the application of natural gas (NG) in production and transportation has grown dramatically, representing a long-term, low-cost, domestic, and secure alternative to petroleum-based fuels. Many technological solutions are currently considered on the market or in development, which address the challenge and opportunity of NG. In this paper, a decision support system (DSS) is introduced for selecting the best fuel to develop in the value chain of NG through four options, namely compressed NG (CNG), liquefied NG (LNG), dimethyl ether (DME), and gas-to-liquids (GTL). The DSS includes a model which uses the technique for order performance by similarity to ideal solution (TOPSIS) to select the best fuel in the value chain of NG based on the attributes such as market situations, technology availability, and transportation infrastructure. The model recommends some key guidelines for two branches of countries, i.e. those which have NG resources and the others. We believe that applying the proposed DSS helps the oil and gas/energy ministries in a most effective and productive manner dealing with the complicated fuel-related production and transportation decision-making situations.