An easy synthesis of photochromic vinylnaphthofurans by the acid-catalyzed one-pot reaction of naphthols with but-2-yne-1,4-diols is described. These uncolored polyaromatic compounds are activated by UV light, at room temperature, and converted through a stilbene-type electrocyclization into a thermally stable orange species, which can be switched back using visible light. The behavior of these photoswitches was elucidated using NMR, which allowed to identify the photoisomers and some side-products, formed after prolonged UV irradiation.