The high toxicity of phosphine and the use of organophosphines as nerve agent precursors has provoked the requirement for a rapid and reliable detection methodology for their detection. Herein, we demonstrate that a ferrocene-derived molecular probe, armed with an azidobenzene trigger, delivers a ratiometric electrochemical signal selectively in response to organophosphorus(III) compounds and can be accurately measured with an inexpensive, handheld potentiostat. Through an intensive assay optimization process, conditions were found that could determine the presence of a model organophosphine(III) nerve agent precursor within minutes and achieved a limit of detection for triphenylphosphine of just 13 ppm. Due to the portability of the detection system and the excellent stability of the probe in solution, we envisaged that this proof-of-concept of work could easily be taken into the field to enable potentially toxic organophosphorus(III) compounds to be detected at the point-of-need.