Liao's photoacids (PAs) are a well-known type of visible light-responsive photoswitches. Here, taking advantage of the temperature-dependent thermal relaxation from the ring-closed to the ring-opened forms, PAs are proposed for the first time as a fluorescent temperature sensor in cells. The logarithmic lifetime (ln τ) of the ring-closed spiro-form exhibited an excellent linear response to the reciprocal of the temperature. In addition, the fluorescent ring-opened PAs were able to highlight lysosomes and responded to lysosomal pH changes. These properties made the PAs promising fluorescent probes in the sensing of subcellular pH and temperature.