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Phosphate oxyanions play central roles in biological, agricultural, industrial, and ecological processes. Their high hydration energies and dynamic properties present a number of critical challenges limiting the development of sensing technologies that are cost‐effective, selective, sensitive, field‐deployable, and which operate in real‐time within complex aqueous environments. Here, a strategy that enables the fabrication of an electrolyte‐gated organic field‐effect transistor (EGOFET) is demonstrated, which overcomes these challenges and enables sensitive phosphate quantification in challenging aqueous environments such as seawater. The device channel comprises a composite layer incorporating a diketopyrrolopyrrole‐based semiconducting polymer and a π‐conjugated penta‐t‐butylpentacyanopentabenzo[25]annulene “cyanostar” receptor capable of oxyanion recognition and embodies a new concept, where the receptor synergistically enhances the stability and transport characteristics via doping. Upon exposure of the device to phosphate, a current reduction is observed, consistent with dedoping upon analyte binding. Sensing studies demonstrate ultrasensitive and selective phosphate detection within remarkably low limits of detection of 178 × 10⁻¹²m(17.3 parts per trillion) in buffered samples and stable operation in seawater. This receptor‐based doping strategy, in conjunction with the versatility of EGOFETs for miniaturization and monolithic integration, enables manifold opportunities in diagnostics, healthcare, and environmental monitoring.

Conductive polymers largely derive their electronic functionality from chemical doping, processes by which redox and charge‐transfer reactions form mobile carriers. While decades of research have demonstrated fundamentally new technologies that merge the unique functionality of these materials with the chemical versatility of macromolecules, doping and the resultant material properties are not ideal for many applications. Here, it is demonstrated that open‐shell conjugated polymers comprised of alternating cyclopentadithiophene and thiadiazoloquinoxaline units can achieve high electrical conductivities in their native “undoped” form. Spectroscopic, electrochemical, electron paramagnetic resonance, and magnetic susceptibility measurements demonstrate that this donor–acceptor architecture promotes very narrow bandgaps, strong electronic correlations, high‐spin ground states, and long‐range π‐delocalization. A comparative study of structural variants and processing methodologies demonstrates that the conductivity can be tuned up to 8.18 S cm⁻¹. This exceeds other neutral narrow bandgap conjugated polymers, many doped polymers, radical conductors, and is comparable to commercial grades of poly(styrene‐sulfonate)‐doped poly(3,4‐ethylenedioxythiophene). X‐ray and morphological studies trace the high conductivity to rigid backbone conformations emanating from strong π‐interactions and long‐range ordered structures formed through self‐organization that lead to a network of delocalized open‐shell sites in electronic communication. The results offer a new platform for the transport of charge in molecular systems.