Storage duration critically shapes the characteristic sweet and mellow quality of ripened pu-erh tea (RPT), yet the underlying chemical mechanisms remain poorly understood. This study investigated the sensory and chemical evolution of a representative commercial RPT product across a nine-year storage gradient (1, 3, 5, 7, and 9 years) by integrating Quantitative Descriptive Analysis (QDA), chromaticity measurement, targeted quantification of 42 non-volatile components, and Headspace Gas Chromatography–Mass Spectrometry (HS-GC-MS) volatilomics with multivariate statistical modeling. Prolonged storage drove systematic sensory maturation: the stale aroma gradually purified, and the taste profile transitioned significantly from heavy and mellow to sweet and mellow (p < 0.05), accompanied by a deepening infusion color with increased redness and yellowness indices. Targeted chemical profiling revealed significant decreases in total polyphenols and astringent esterified catechins, particularly epicatechin gallate (ECG) and epigallocatechin gallate (EGCG) (p < 0.05), while theabrownins remained stable and soluble sugars peaked at intermediate storage stages. Pearson correlation analysis linked these chemical shifts to sensory perception, with enhanced sweetness, mouthfeel thickness strongly associated with reduced monomeric catechins and free amino acids (p < 0.001). Volatilomics combined with K-means clustering and relative odor activity value (ROAV) analysis revealed a dual mechanism of flavor refinement: progressive accumulation and increasing odor activity of aged aroma markers (1,2,3-trimethoxybenzene, β-ionone) coupled with systematic attenuation of pungent acids and grassy aldehydes. These findings, based on a single, standardized commercial product, elucidate the chemical-sensory foundation of the sweet and mellow profile in aged RPT and provide candidate markers and a transferable analytical framework for quality assessment of stored teas.