Organic room temperature phosphorescence (RTP) systems are rarely reported for vapor phase sensing due to the contradiction between vapor permeability and phosphorescence ability. Till now, almost all reported works are based on ″turn-off″ mode RTP detection by destroying the compact-packaging oxygen-free environment. ″Turn-on″ mode RTP detection owns additional anti-interference capability due to a lower initial RTP background signal, while its realization is even harder. In this research, in situ phosphorescence ″turn-on″ sensing was realized for methamphetamine (MPEA) vapor detection. Based on the formation of aromatic phenolic aldehyde-secondary amine ion pairs with air-stable RTP performance, the fluorescent tri-formyl phenol (TFP) film was converted into a stable RTP state after being exposed to the MPEA vapor, as supported by nuclear magnetic resonance (NMR) and mass spectrometry together with theoretical calculations. The red-shifted absorption and emission, enhanced emission intensity, and 49.7 μs phosphorescence lifetime allowed multiple mode MPEA vapor sensing from chromaticity to fluorescence to phosphorescence. The lifetime mode detection limit reached 0.4 ppt, 5 orders of magnitude lower than the intensity mode detection limit of 20.3 ppb.