Photoremovable protecting groups (photocages) 6b-6i based on 1-amino-2-hydroxymethylnaphthalene were developed, and their applicability to release alcohols and carboxylic acids in photohydrolysis was investigated. Compound 6b cannot release alcohol since N-demethylation takes place instead. However, the photorelease of carboxylic acids from 6c-6i was demonstrated on caged substrates, including some nonsteroidal drugs and a neurotransmitter. A simultaneous use of aniline and aminonaphthalene cages allows for the chromatic orthogonality and selective deprotection by UV-B or near-visible and UV-A light, respectively. The photochemical reaction mechanism of decaging was investigated by fluorescence measurements and laser flash photolysis, indicating that the heterolysis and elimination of carboxylic acids take place in the singlet excited state, delivering carbocation as an intermediate. The photoheterolysis in the singlet excited state, which directly releases caged substrates, is highly applicable for the photocages and has advantages compared to hitherto used nitrobenzyl derivatives.