The synthesis of spiropyran dyes exhibiting solvent-driven isomerization even in the dark condition is an important subject for the design of optical materials. A conventional synthesis strategy involves the conjugation of indoline moieties with electron-deficient aromatic moieties. Herein, we report that a spiropyran conjugated with a hydroxynaphthalene moiety (1) is a new member exhibiting solvent-driven isomerization, even bearing an electron-donating −OH moiety. The dye exists as a colorless spirocyclic (SP) form in nonpolar media. It, however, shows a blue color in polar media, especially in aqueous media, due to the formation of ring-opened merocyanine (MC) forms, where the isomerization terminates in 10 s even at room temperature. The spontaneous SP → MC isomerization originates from the MC forms stabilized by the highly delocalized π-electrons on the hydroxynaphthalene moiety. The solvation in polar media and the hydrogen bonding interaction with water molecules decrease the ground-state energy of the MC forms, triggering spontaneous isomerization. The dye exhibits two MC absorption bands assigned to the trans–trans–cis (TTC) and cis–trans–cis (CTC) isomers. The absorbance of the CTC band increases more significantly with an increase in the water content, and the increase exhibits a linear relationship with a hydrogen-bond donor acidity of solvents. The phenolate oxygen of the CTC form has larger hydrogen-bond acceptor basicity, resulting in stronger stabilization by the water molecule.