Water resources are under pressure because of human activities. Its management faces the challenge of enhancing long-term water security while minimizing undesirable economic, social, and environmental impacts along with its production chain. Since water and wastewater treatment plants are designed to maintain and conserve freshwater provisioning services, it is paramount to understand how it operates before proposing options for sustainability. At this point, the diagnosis phase claims for methods scientifically-based, systemic, and more objective to provide information for decision-makers towards strategic management of water resources. This work applies the five-sector sustainability model (5SenSu) to assess Brazil's twenty major water and wastewater treatment companies (WWTC) to quantify their sustainability levels that allow ranking procedures and the establishment of benchmarks for improvements. Under comparative basis, results identified the top-three sustainable companies, CORSAN, CASAN, and SANEPAR, which should be considered examples of best practices. Specifically, the following best-ranked companies in each sector within 5SenSu should be used as benchmark patterns for more oriented best practices: SANEAGO, sector 1; AGESISA, sector 2; CORSAN, sector 3; CASAL, sector 4; MA, sector 5. This work contributes to the advancement in modeling sustainability assessment of human-managed systems (applied in WWTCs in this present study) from a systemic and epistemologically rooted approach, avoiding shortcomings and misleading discussions on the sustainability issue. Quantifying sustainability of WWTCS from 5SenSu allows the identification of those sectors/indicators that requires immediate cleaner production practices by decision-makers to improve overall sustainability, besides identifying those companies more aligned with the requirements of UN SDGs.