The organic photoelectrochemical transistor (OPECT) biosensing relies solely on a singular signal readout inherently, which restrains the precision and dependability nestled within pertinent biological measurements. Herein, a high‐precision magnetic assisted OPECT and smartphone colorimetric (SCL) dual‐mode biosensing platform is first established for detecting harmful algal toxin okadaic acid (OA) by biocatalytic reaction. MXene@SnO2‐Ce‐MOF (MXSnO/Ce‐MOF) Z‐scheme heterojunctions with abundant oxygen vacancies are prepared as photoactive materials. Initially, in the presence of OA, the coupling of trigger DNA (tDNA) to magnetic beads (MBs) via anchor DNA (aDNA) is released through the interaction of the target analyte with the aptamer. Subsequently, the carried tDNA triggers HCR between the two hairpin sequences, producing long double helix chains to capture glucose oxidase (GOx). The obtained GOx supernatant catalyzes glucose to produce H2O2, which can oxidize Ce‐MOF, leading to the alteration of electrode color and a significant decrease in the overall photocurrent of MXSnO/Ce‐MOF. Crucially, the novel OPECT‐SCL biosensor exhibits excellent sensitivity and precision, boasting detection thresholds as low as 42.9 pM and 1.2 nM, respectively, and accomplishes the automated detection of OA within real samples. The proposed OPECT‐SCL dual‐signal measurement model constitutes a sensitive, portable, and precise platform for the quantification of marine toxins.