To the best of our knowledge, very few works have been done for the continuous real-time monitoring of Proton Exchange Membrane Fuel Cells (PEMFCs) membrane degradation based on fluoride-specific electrochemical microsensors. PEMFCs are eco-smart energy sources for efficient transportation but experience variable degradation rates that wear the Membrane Electrode Assembly (MEA), a critical component of the fuel cell’s functionality. Current market options lack specific diagnostics and a legitimate indication of when exactly the membrane needs to be replaced. As such, this work focused on manufacturing a sensor for measuring MEA degradation in real-time by selectively monitoring fluoride concentration in effluent water, a signature PEMFCs degradation status, through functionalized LaF3:(Au nanoparticle) thin films (∼60 nm). The sensor’s exceptional specificity/sensitivity has been achieved in real-time at a sub 10 ppb level, optimized through spin-coating deposition and post-annealing process. Its multimodal readout has been achieved and studied through the characterizations of open circuit potential, cyclic voltammetry, chronoamperometry, and differential pulse voltammetry revealing a consistent linear decrease of 15.7 mA cm−2 at 0 ppb to 10.2 mA cm−2, while also maintaining its low-cost, small size, and robustness.