This article discusses the configuration of specialized healthcare networks and aims to analyze the potential for optimization of geographic access in the chemotherapy network of the Brazilian Unified National Health System (SUS) in Rio Grande do Sul State, Brazil, using linear programming. The study used ex post facto mathematical modeling with an analytical objective and a qualitative-quantitative approach, using data collection and literature and document searches as the procedures. The potential for optimization was assessed by the percentage difference between the total distances traveled under the current situation and the optimum solution obtained. The results with the optimized situation included a decrease of 293,246km (14.4%) in the total monthly distance traveled in the network, or a mean reduction of 13.02km per procedure performed, compared to the current distance traveled. This gain would be obtained by redistribution of the municipalities of origin and the referral services' capacity to supply procedures. The results point to great potential for optimization of the target network, proving that linear programming can provide technical support for the configuration of new specialized thematic healthcare networks and optimization of the existing networks.