Lake eutrophication, often driving harmful algal blooms (HABs) and ecosystem degradation, involves complex biogeochemical shifts within sediments. Changes in the sedimentary dissolved organic matter (DOM) composition during transitions from macrophyte to algal dominance are thought to critically regulate internal phosphorus (P) loading, yet the underlying mechanisms, especially in vulnerable plateau lakes like Qilu Lake, require further elucidation. This study investigated the coupled cycling of carbon (C) and P in response to historical ecosystem succession and anthropogenic activities using a 0–24 cm sediment core from Qilu Lake. We analyzed the total organic carbon (TOC), total phosphorus (TP), sequential P fractions, and DOM fluorescence characteristics (EEM-PARAFAC), integrated with chronological series data. The results revealed an asynchronous vertical distribution of TOC and TP, reflecting the shift from a submerged macrophyte-dominated, oligotrophic state (pre-1980s; high TOC, low TP, stable Ca-P dominance) to an algae-dominated, eutrophic state. The eutrophication period (~1980s–2010s) showed high TP accumulation (Ca-P and NaOH85 °C-P enrichment), despite a relatively low TOC (due to rapid mineralization), while recent surface sediments (post-2010s) exhibited a high TOC, but a lower TP following input controls. Concurrently, the DOM composition shifted from microbial humic-like dominance (C1) in deeper sediments to protein-like dominance (C3) near the surface. This study demonstrates that the ecosystem shift significantly regulates P speciation and mobility by altering sedimentary DOM abundance and chemical characteristics (e.g., protein-like DOM correlating negatively with Ca-P), reinforcing a positive feedback mechanism that sustains internal P loading and potentially exacerbates HABs. DOM molecular characteristics emerged as a key factor controlling the internal P cycle in Qilu Lake, providing critical insights for managing eutrophication in plateau lakes.