A novel 7a,8,10,1':2,3][1,3]-oxazino [6,5,4-ij]isoquinoline derivative (POIQ) is accidentally obtained from an isoquinoline derivative and iodine in dimethyl sulfoxide, which is demonstrated to undergo a mechanism of demethylation and thus intramolecular nucleophilic substitution. POIQ with twisted molecular conformation and loose stacking arrangement shows multifunctional optical properties including dual-state emission, mechanochromic, and solid-state acidochromic activities. Furthermore, an organic room temperature phosphor-escence (RTP) doped system with green afterglow of 2 s is constructed using POIQ as the guest and easily available phenyl benzoate as the host, in which the host molecules assist in the transfer of the triplet excitons of the guest molecules. Rewritable optical recording media and information encryption are also realized based on multifunctional optical properties of this compound. This work provides inspiration for the development of N,O-containing fused-ring compounds with fluorescence/RTP properties.