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This application relates to the field of biomedical sensing and wearable health monitoring technology, and discloses a photoelectrochemical sensing microneedle and its preparation method, monitoring system, and detection method. The sensing microneedle comprises a swellable dual-network hydrogel microneedle matrix, a three-dimensional conductive network composed of high aspect ratio metal nanowires with localized surface plasmon resonance effect, and a semiconductor nanostructure composited on the surface of the metal nanowires to form a Schottky heterojunction. The mechanical constraint of the rigid polymer framework and the high aspect ratio of the metal nanowires synergistically ensure the continuity of the conductive network in the swelled state. Under excitation light irradiation, hot electrons migrate through the built-in electric field of the Schottky junction to the semiconductor surface to generate reactive oxygen free radicals. These free radicals then non-enzymatically catalyze the oxidation of target analytes in the interstitial fluid under zero or low bias voltage, generating a photocurrent signal, thus integrating minimally invasive sampling with in-situ highly selective detection.