Mellow and thick taste (MTT) is considered to be a typical taste characteristic of high-quality Pu-erh ripe tea. However, the role of polysaccharide conjugates remains unclear. In this study, the infusion of different grades of Pu-erh ripe tea was isolated to fractions by sensory-guided ultrafiltration technology and the key taste substances of MTT in Pu-erh ripe tea were identified and confirmed in the sensory reconstruction experiment. Further separation, purification and structural identification of the polysaccharide conjugates were carried out. Involving in aggregation morphology, the ultrafiltration fraction exhibited obvious MTT than other fractions. The main MTT compound (PRTPS-5), mainly composed of the rhamnose, galactose, arabinose and mannose, had a molecular weight of 22.93 kDa. The main chain of PRTPS-5 comprised α-L-Araf-(1→, →2,4)-α-L-Rhap-(1→, →2)-α-L-Rhap-(1→, α-D-Galp-(1→, →4)-α-D-GalpA-6-OMe-(1→, →4)-α-D-Manp-(1→, →3,6)-β-D-Galp-(1 → and →5)-α-L-Araf-(1 → and contained multiple pectic characteristic peaks. This result had scientific guiding significance for the quality enhancement of Pu-erh ripe tea.