Rapid and reliable detection of organophosphorus (OP) threats is essential for facilitating efficient and timely countermeasures. This work describes the design and operation of a miniaturized electrochemical sensor array chip, based on strategic coupling of diverse MOF-based biomimetic and biocatalytic reagent layers (offering tunable OP target specificities) with different potentiometric, voltametric, and amperometric transducers to generate information-rich analytical data and robust discrimination power towards rapid field identification of key classes of OP threats. This uniquely integrated 4-electrode sensor array yields rich analytical data that enables rapid and efficient discrimination of P−F- and P−Cl-type OP nerve agents (NAs) and OP pesticides from coexisting environmental pollutants. The sensor array outputs lead to distinct binary codes for the target OP threats that enable their rapid digital identification. This sensor array chip thus presents a significant advance towards reliable OP threat-sensing hand-held devices that meet the urgent demands of different defense surveillance applications. © 2022 Wiley-VCH GmbH.