The sustainable development and consumption need more efficient use of natural resources. As a consequence, the use of industrial solvents demands their recovery instead of end-of-pipe treatment. It is not always clear, however, which treatment alternative should be applied. Based on an industrial case study, the environmental and economic evaluation and comparison of the treatment alternatives of a non-ideal solvent mixture containing azeotropes is investigated for determining the preferable option. For the recovery of the industrial solvent mixture, two different separation alternatives are evaluated: a less effective alternative and a novel design based on hybrid separation tools. An end-of-pipe treatment alternative, incineration, is also considered and the split of the solvent mixtures between recovery and incineration is investigated. The environmental evaluation of the alternatives is carried out using ‘Eco-indicator 99 life-cycle impact assessment methodology’. Economic investigation is also accomplished. The economic features clearly favour the total recovery, however, the environmental evaluation detects that if a recovery process of low efficiency is applied, its environmental burden can be similar or even higher than that of the incineration. This motivates engineers to design more effective recovery processes and reconsider the evaluation of process alternatives at environmental decision making.