(1) Background: Ionotropic gelation of cost-effective and eco-friendly biopolymer chitosan (Chit) is a novel and promising approach to the one-step synthesis of proton-conducting fuel cell bio-membranes.The method discovered by the author in 2011 and subsequently drowned among very few papers. This work aimed to relaunch this method through clear and effective communication of new unpublished results emphasizing the key aspects of this topic for successful dissemination of the results and significant future developments. (2) Methods and results: The mechanism of in-situ ionotropic gelation of Chit on an alumina substrate by phosphotungtate anions (PWA) was discussed and analyzed. The study sheds light on the effect of prolonged post-treatment in phosphotungstic acid (PWA) solution on the obtained chitosan/phosphotungstate (Chit-PWA) flat structures. Methods used included combined structural (XRD), thermal-gravimetric (DTG), electrochemical (in-situ EIS), compositional (EDX),morphological analysis (SEM), as well as the performances in a low temperature H/O fuel cell(4) Conclusions: This contribution discloses novel possibilities aimed at increasing the impact of ionotropic gelation of chitosan on the scientific community working on the synthesis of novel proton conductive bio-composite membranes and structures.