Despite the existence of several waste recycling initiatives in Brazil, the national average of recyclable material recovery rates still remains below 3%. In this context, it is necessary to diagnose the performance of systems to implement improvement actions, considering the particularities of each system. In this study, we describe the application of a method capable of diagnosing the effectiveness of selective collection systems by identifying a general sustainability index, calculated based on 16 performance indicators. The study focused on the city of Volta Redonda and was organized into three stages: identification of the performance evaluation method; data collection and calculation of indicators; and calculation of the sustainability index. The index value found for the city was 0.47, which represents an unfavorable level of sustainability. In this case, Volta Redonda is making insufficient investments in its selective waste collection system. The factors that contributed to this low index are: an outdated solid waste management plan, low collection coverage, low recovery rate of recyclable materials, high rejection rate, high selective collection cost, outdated cost of selective collection service, precarious occupational health and safety conditions of members of waste picker cooperatives, and lack of registration of residences for donation of recyclable materials.