As a consequence of the increase in reverse osmosis (RO) desalination plants, the number of discarded RO modules for 2020 was estimated to be 14.8 million annually. Currently, these discarded modules are disposed of in nearby landfills generating high volumes of waste. In order to extend their useful life, in this research study, we propose recycling and reusing the internal components of the discarded RO modules, membranes and spacers, in membrane engineering for membrane distillation (MD) technology. After passive cleaning with a sodium hypochlorite aqueous solution, these recycled components were reused as support for polyvinylidene fluoride nanofibrous membranes prepared by electrospinning technique. The prepared membranes were characterized by different techniques and, finally, tested in desalination of high saline solutions (brines) by direct contact membrane distillation (DCMD). The effect of the electrospinning time, which is the same as the thickness of the nanofibrous layer, was studied in order to optimize the permeate flux together with the salt rejection factor and to obtain robust membranes with stable DCMD desalination performance. When the recycled RO membrane or the permeate spacer were used as supports with 60 min electrospinning time, good permeate fluxes were achieved, 43.2 and 18.1 kg m−2 h−1, respectively; with very high salt rejection factors, greater than 99.99%. These results are reasonably competitive compared to other supported and unsupported MD nanofibrous membranes. In contrast, when using the feed spacer as support, inhomogeneous structures were observed on the electrospun nanofibrous layer due to the special characteristics of this spacer resulting in low salt rejection factors and mechanical properties of the electrospun nanofibrous membrane.