In developing countries like Colombia, trucking is the primary transportation system for goods, becoming one of the most critical actors in pollution generation within the supply chain. This transportation system and its implications are the focus of study in public health, environmental, planning, and economic scenarios due to the negative externalities of pollution. The affection of human beings and ecosystems gives relevance to the necessity of understanding and controlling emissions in a country where the topography and high longitudinal slope increase fuel consumption and the emissions released by trucking. The authors analyzed carbon dioxide (CO2) emissions produced by intercity trucking trips of the most representative movement in Colombia, using secondary information gathered from the Colombian Logistics Portal (CLP), an information system from the Colombian Department of Transportation (CDOT). The Ordinary Least Squares (OLS) technique generated linear and non-linear econometric models to estimate CO2 emissions between any Origin-Destination (O-D) pair, considering as explanatory variables traveled distance, roadway slope, and cargo movement, getting emission generation models (EGM) which represent accurately the terrain reality and the pollution scheme. This research aims to complement and generate information about pollution by freight transportation in Colombia for future forecasting and support of policymaking oriented to sustainable transportation. Based on laws and sustainable regulations, transportation planners, decision-makers, and associated sectors are provided analyses about freight policy outcomes.