Removing nitrogen from wastewater by conventional treatment methods requires substantial energy, only to release it back to the atmosphere as gaseous nitrogen. Herein, we investigated the applicability of membrane distillation (MD) in resource recovery from sludge digestate by controlling the volatility and pressure of the vapor transport across the membrane to concentrate ammonia in the permeate stream. A mixture of Nafion ionomer and Multiwall Carbon Nanotubes (MWCNTs) were incorporated into a Poly (vinylidene fluoride-co-hexafluoropropene; PVDF-HFP) nanofiber matrix to fabricate a nanoporous honeycomb Nafion membrane featuring high recovery and increased mechanical strength. Theoretical modeling was conducted to predict the expected performance of the fabricated Nafion membrane under different operation conditions and to reveal the mechanism behind the enhanced recovery of Nafion membranes in the MD process. The resultant Nafion (8%)/MWCNT (2.5%)/PVDF-HFP nanofibrous membrane showed up to three times higher ammonia recovery compared to the commercial PVDF membrane from a feed with an ammonia concentration of 300 mg/L. The theoretical analysis quantitatively revealed that the Nafion containing membrane can not only suppress the negative effect of membrane's structural resistance on the ammonia recovery efficiency but also enhance the efficiency. In addition, we also uncovered that the effect of Nafion on ammonia recovery efficiency was maximized when the Nafion 8% membrane was employed. This study demonstrated an innovative and realistically applicable MD treatment process for recovering resource, which integrates low-grade heat and has scaling-up potential for wastewater treatment plants.