The fast-growing population in Vientiane, the capital of Laos, has resulted in increasing domestic wastewater generation, which directly impacts the urban water environment due to the lack of a suitable wastewater treatment system. This study aims to assess six wastewater treatment alternatives based on two technologies—trickling filter and activated sludge—used for on-site, decentralized, and centralized wastewater treatment systems to support decision-making for selecting the most suitable and practical alternative for wastewater treatment in Vientiane. To determine the most appropriate treatment system, the wastewater treatment process simulation with BioWin and the technique for order preference by similarity to ideal solution (TOPSIS) method are applied to assess the removal efficiencies for biochemical oxygen demand (BOD), chemical oxygen demand (COD), and total suspended solids (TSS), as well as to rank the six wastewater treatment technologies based on the following four environmental criteria: (1) land requirement, (2) electricity use, (3) sludge production, and (4) CO2 emissions. The BioWin results illustrate that the capacity of each alternative is similar in terms of domestic wastewater treatment efficiency, while differing in terms of environmental impacts. In addition, the alternative ranking shows that a centralized wastewater treatment system with a trickling-filter process is more suitable than on-site and decentralized wastewater treatment systems based on their environmental impacts. This finding provides evidence for decision-makers to select a suitable alternative for wastewater treatment in order to promote access to safe sanitation and sustainable urban wastewater management in Vientiane, Laos.