Differential Pulse Voltammetric Analysis of the New Psychoactive Drug 3β‐(4‐Fluorobenzoyloxy)tropane (fluorotropacocaine)

3β‐(p‐Fluorobenzoyloxy)tropane (fluorotropacocaine, pFBT) is an emerging new psychoactive substance (NPS) structurally related to cocaine and increasingly detected in products purchased online. The rapid diversification of NPS calls for analytical workflows that are both selective and readily deployable for seized materials and biological matrices. Here, we report a comprehensive electrochemical characterization of pFBT in an ethanol/LiClO 4 medium using cyclic voltammetry, differential pulse voltammetry (DPV), chronoamperometry at macroelectrodes, and rotating‐disk electrode measurements, and we translate the mechanistic and kinetic findings into a DPV‐based method for pFBT determination. Under optimized conditions, DPV provided an LOQ of 0.20 µg mL −1 and a dynamic range up to 150 µg mL −1 . The method was applied to a simulated “street tablet” matrix and to fortified synthetic and human urine samples, showing good selectivity toward common excipients and typical coformulants as well as co‐occurring amine‐containing NPS (xylazine and nitracaine). For urine analysis, Florisil‐based solid‐phase extraction (SPE) was implemented for clean‐up and enrichment; Design of Experiments (DoE) optimization afforded enrichment factors up to 50× and enabled quantification down to 0.050 µg mL −1 in fortified urine. Recoveries between 79% and 105% across the investigated matrices support the applicability of the proposed workflow to forensic and clinical toxicology contexts.