Natural polyphenols have drawbacks such as instability and low bioavailability, which can be overcome by encapsulated slow-release systems. Natural polymer hydrogels are ideal materials for slow-release systems because of their high biocompatibility. In this study, Longzhua mushroom polysaccharide hydrogel (LMPH) was used to encapsulate rambutan peel polyphenols (RPP) and delay their release time to improve their stability and bioavailability. The mechanical properties, rheology, stability, swelling properties, water-holding capacity, RPP loading, and slow-release behavior of LMPH were investigated. The results showed that LMPH has adequate mechanical and rheological properties, high thermal stability, excellent swelling and water-holding capacity, and good self-healing behavior. Increasing the polysaccharide content not only improved the hardness (0.17–1.13 N) and water-holding capacity of LMPH (90.84–99.32%) but also enhanced the encapsulation efficiency of RPP (93.13–99.94%). The dense network structure slowed down the release of RPP. In particular, LMPH5 released only 61.58% at 48 h. Thus, a stable encapsulated slow-release system was fabricated using a simple method based on the properties of LMPH. The developed material has great potential for the sustained release and delivery of biologically active substances.