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Abstract Photochemistry is a fundamental process of planetary atmospheres that regulates the atmospheric composition and stability¹. However, no unambiguous photochemical products have been detected in exoplanet atmospheres so far. Recent observations from the JWST Transiting Exoplanet Community Early Release Science Program^2,3found a spectral absorption feature at 4.05 μm arising from sulfur dioxide (SO₂) in the atmosphere of WASP-39b. WASP-39b is a 1.27-Jupiter-radii, Saturn-mass (0.28 M_J) gas giant exoplanet orbiting a Sun-like star with an equilibrium temperature of around 1,100 K (ref. ⁴). The most plausible way of generating SO₂in such an atmosphere is through photochemical processes^5,6. Here we show that the SO₂distribution computed by a suite of photochemical models robustly explains the 4.05-μm spectral feature identified by JWST transmission observations⁷with NIRSpec PRISM (2.7σ)⁸and G395H (4.5σ)⁹. SO₂is produced by successive oxidation of sulfur radicals freed when hydrogen sulfide (H₂S) is destroyed. The sensitivity of the SO₂feature to the enrichment of the atmosphere by heavy elements (metallicity) suggests that it can be used as a tracer of atmospheric properties, with WASP-39b exhibiting an inferred metallicity of about 10× solar. We further point out that SO₂also shows observable features at ultraviolet and thermal infrared wavelengths not available from the existing observations.