In recent years, cadmium sulfide (CdS) has been widely investigated due to its excellent photocatalytic performance. However, its practical application in pollutant treatment is limited by its narrow photoresponse range and susceptibility to photocorrosion. Herein, we design a unique four-layer core–shell structure NaYF4:Yb3+,Er3+@NaYF4@CdS@Au (CSNPs@CdS@Au), with an inert NaYF4 shell coating on NaYF4:Yb3+,Er3+ (CNPs) to form NaYF4:Yb3+,Er3+@NaYF4 (CSNPs) and CdS depositing on CSNPs (CSNPs@CdS); Au nanoparticles are loaded on CdS (CSNPs@CdS@Au). Compared with CdS (9.81%), CSNPs (5.0%), CSNPs/CdS (6.9%), and CSNPs@CdS (81.0%), CSNPs@CdS@Au degrades 97.7% Rhodamine B (RhB) within 15 min, exhibiting superior photocatalytic performance, attributable to two key factors: (1) the NaYF4 inert shell encapsulation amplifies upconversion (UC) luminescence intensity by suppressing surface quenching; and (2) the electron transfer between Au nanoparticles and CdS effectively promotes spatial separation of photogenerated charge carriers and increases reactive active sites. Additionally, after five degradation cycles, CSNPs@CdS@Au still maintains a 93.25% degradation rate for RhB, confirming its excellent stability. This remarkable stability is attributed to the uniquely designed multilayer core–shell architecture, which significantly enhances structural integrity through physical isolation effects. This study establishes a material preparation strategy for efficient photocatalytic pollutant degradation.