Stimulus-responsive room-temperature phosphorescence (RTP) materials have gained significant attention for their important optoelectronic application prospects. However, the fabrication strategy and underlying mechanism of stimulus-responsive RTP materials remain less explored. Herein, we present a reliable strategy for achieving pH-responsive RTP materials by integrating poly(vinyl alcohol) (PVA) with carboxylic acid or amino group functionalized terpyridine (Tpy) derivatives. The resulting Tpy derivatives-based RTP materials displayed reversible changes in emission color, intensity, and lifetime of both prompt and delayed emission. Notably, the RTP emission undergoes a significant diminish upon exposure to acid due to the protonation of Tpy units. Taking advantage of the decent RTP emission and pH-responsiveness of these RTP films, a spatial-time-resolved anti-counterfeiting application is demonstrated as a proof-of-concept for largely enhancing the security level. This study not only provides new prospects for developing smart RTP materials but also promotes the advancement of optical anti-counterfeiting applications.