Rising global concerns posed by chemical and biological threat agents highlight the critical need to develop reliable strategies for the real-time detection of such threats. While wearable sensing technology is well suited to fulfill this task, the use of on-body devices for rapid and selective field identification of chemical agents is relatively a new area. This work describes a flexible printed textile-based solid-contact potentiometric sensor for the selective detection of fluoride anions liberated by the biocatalytic hydrolysis of fluorine-containing G-type nerve agents (such as sarin or soman). The newly developed solid-contact textile fluoride sensor relies on a fluoride-selective bis(fluorodioctylstannyl)methane ionophore to provide attractive analytical performance with near-Nernstian sensitivity and effective discrimination against common anions, along with excellent reversibility and repeatability for dynamically changing fluoride concentrations. By using stress-enduring printed inks and serpentine structures along with stretchable textile substrates, the resulting textile-based fluoride sensor exhibits robust mechanical resiliency under severe mechanical strains. Such realization of an effective textile-based fluoride-selective electrode allowed biosensing of the nerve-agent simulant diisopropyl fluorophosphate (DFP), in connection to immobilized organophosphorus acid anhydrolylase (OPAA) or organophosphorus hydrolase (OPH) enzymes. A user-friendly portable electronic module transmits data from the new textile-based potentiometric biosensor wirelessly to a nearby smartphone for alerting the wearer instantaneously about potential chemical threats. While expanding the scope of wearable solid-contact anion sensors, such a textile-based potentiometric fluoride electrode transducer offers particular promise for effective discrimination of G-type neurotoxins from organophosphate (OP) pesticides, toward specific field detection of these agents in diverse defense settings. © 2021