Sensor technology, particularly disposable, field-deployable devices offer considerable promise for addressing major security demands, in general, and in particular the urgent needs for selective and rapid field detection of highly toxic G-type organophosphate (OP) nerve agents. Herein, we report on the first example of a disposable electrochemical biosensor chip for decentralized field detection of diisopropyl fluorophosphate (DFP), as the simulant compound of G-type nerve agents (e.g., Sarin and Soman), based on the integration of an all-solid-state fluoride potentiometric transducer with the enzyme organophosphorus acid anhydrolase (OPAA) in connection to a hand-held potentiometric analyzer. Such solid-contact fluoride ion-selective electrodes were realized by comparing different fluoride ionophores to select the bis(fluorodioctylstannyl)methane molecule, along with systematic optimization of the experimental parameters. This first solid-contact fluoride detection chip displayed a favorable analytical performance, with near-Nernstian behavior at neutral pH in different buffers, high selectivity against various anions along with excellent reproducibility. Combining such desirable merits of the new fluoride sensor with the selective biocatalytic hydrolysis via an immobilized OPAA, to break the P[sbnd]F bond of G-type neurotoxins and release detectable fluoride ions, thereby enabled an attractive analytical performance. Both the fluoride and the nerve-agent recognition layers have thus been systematically optimized. The resulting biosensor chip thus displays a fast, sensitive and selective response towards DFP (including efficient discrimination against OP pesticides), along with a wide dynamic range of 250–3000 μM. Key challenges towards developing the nerve-agent detection chip were carefully addressed, including the pH incompatibility of the enzymatic and detection processes. By providing effective discrimination against common OP pesticides and minimizing related false alarms, the resultant disposable potentiometric biochip platform is expected to provide an instantaneous reliable warning of chemical attack and exposure towards a timely countermeasure action, and hence, would dramatically advance the protection of our military personnel. © 2020 Elsevier B.V.