Fuel transportation constitutes a significant portion of hazardous materials transportation for decades. Fuel companies generally prefer highway transportation whereas railway transportation is also a potential alternative due to its advantages both from cost- and risk perspectives. The aim of this thesis is to investigate the potential benefits of using railways in conjunction to highways for fuel transportation in Turkey. In this thesis, we first investigate a quantitative risk model that could be used to assess the risk of railway transportation. Then, a mathematical model is developed which aims to answer the following three questions: What should be the routes of fuel products transported from suppliers to demand points and which transportation mode(s) should be used on these routes?, Where to open transfer units?, and Which suppliers should satisfy which demand points with what capacity?. The model has two possibly conflicting objectives of minimizing the total transportation risk and minimizing the total transportation cost. The proposed models are tested over Turkish network for which all required realistic data are collected.