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Abstract We report an unusual photochromic behavior of 4,4′‐disubstituted‐2,2′‐bipyridine. It was found that in the presence of a SO₃source and HCl, 2,2′‐bipyridine‐4,4′‐dibutyl ester undergoes a color change from yellow to magenta in solution with maximum absorbance at 545 nm upon irradiation with 395 nm light. The photochromism is thermally reversible in solution. Different from the known bipyridine‐based photoswitching pathways, the photo response does not involve any metal which form colored complexes or the formation of colored free radical cations like the photo‐reduction of viologens. A combination of experimental and computational analysis was used to probe the mechanism. The results suggest the colored species to be a complex formed between N‐oxide of the 2,2′‐bipyridine‐4,4′‐dibutyl ester and SO₂; the N‐oxide and SO₂are formed from photoactivated oxidation of the bipyridine with SO₃serving as the oxygen source. This complex represents a new addition to the library of photoswitches that is easy to synthesize, reversible in solution, and of high fatigue resistance, making it a promising candidate for applications in photo‐switchable materials and SO₃detection. We also demonstrated experimentally similar photochromic behaviors with 2,2’‐bipyridine‐containing polymers.