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Freight transportation in Brazil is characterized by the predominance of the road mode. This imbalance in the sector suggests the need to develop efficient strategies that can increase competitiveness of alternative modes. However, in Brazil, there are few studies investigating firms' preferences concerning different attributes of travel modes. This study analyses the travel mode choice decision-making process of shippers in the state of Rio de Janeiro, Brazil. The main objectives of this article are related to model travel mode choice and characterize freight transport in a Brazilian context. Discrete choice models were estimated using Stated Preference data to identify shippers' preferences and discuss some possible sustainable policies that could increase the competitiveness of the railway network. Elasticities and probability marginal effects were computed, and different scenarios were simulated to predict the possible effects of implementing alternative transport policies. Simulation results show that shippers' preferences have low sensitivity to changing factors. [ABSTRACT FROM AUTHOR]