The problem of water scarcity is already serious and risks becoming dramatic in terms of human health as well as environmental safety. Recovery of freshwater by means of eco-friendly technologies is an urgent matter. Membrane distillation (MD) is an accredited green operation for water purification, but a viable and sustainable solution to the problem needs to be concerned with every step of the process, including managed amounts of materials, membrane fabrication procedures, and cleaning practices. Once it is established that MD technology is sustainable, a good strategy would also be concerned with the choice of managing low amounts of functional materials for membrane manufacturing. These materials are to be rearranged in interfaces so as to generate nanoenvironments wherein local events, conceived to be crucial for the success and sustainability of the separation, can take place without endangering the ecosystem. In this work, discrete and random supramolecular complexes based on smart poly(N-isopropyl acrylamide) (PNIPAM) mixed hydrogels with aliquots of ZrO(O2C-C10H6-CO2) (MIL-140) and graphene have been produced on a polyvinylidene fluoride (PVDF) sublayer and have been proven to enhance the performance of PVDF membranes for MD operations. Two-dimensional materials have been adhered to the membrane surface through combined wet solvent (WS) and layer-by-layer (LbL) spray deposition without requiring further subnanometer-scale size adjustment. The creation of a dual responsive nanoenvironment has enabled the cooperative events needed for water purification. According to the MD’s rules, a permanent hydrophobic state of the hydrogels together with a great ability of 2D materials to assist water vapor diffusion through the membranes has been targeted. The chance to switch the density of charge at the membrane–aqueous solution interface has further allowed for the choice of greener and more efficient self-cleaning procedures with a full recovery of the permeation properties of the engineered membranes. The experimental evidence of this work confirms the suitability of the proposed approach to obtain distinct effects on a future production of reusable water from hypersaline streams under somewhat soft working conditions and in full respect to environmental sustainability.