The detection and quantification analysis of silver ions is important to protect human health and improve the level of wastewater treatment. In this work, a polyvinyl alcohol (PVA) hydrogel-based sensing material based on an aggregation-induced emission strategy was developed and combined with a portable laser-induced fluorescence spectroscopy (LIFs) device for the direct detection and quantification of silver ions in water. Considering the requirements of environmental water analysis regarding portability, reliability, and convenience, this fluorescence turn-on strategy was optimized accordingly to ensure the accuracy and stability of the analysis in complex natural water environmental. This sensing method showed operational excellence and good sensitivity (down to 1 ppb) and may provide a stable and convenient strategy for the on-site, real-time analysis of environmental water samples.