A new series of O∧C-chelate tetra-coordinated boranes with naphtha-aldehyde as the chelate backbone have been synthesized. Their photophysical and photochemical properties have been examined, which show that all of the compounds can undergo both photo and thermal transformations, generating aryl-migrated [1,2]oxaborinine derivatives as the major products. 1,3-Sigmatropic shifts and an intramolecular nucleophilic addition mechanism are proposed for the photochemical and thermal conversion pathways, respectively.