Theaflavins (TFs) are naturally bioactive compounds with low stability and poor bioavailability. In this study, the stability of TFs during storage at 25 °C for 21 d and thermal treatments at 65 °C, 85 °C and 105 °C for 0.5–4 h of water in oil (W/O) Pickering emulsions composed of TFs (0–9 mg/g), ursolic acid, oil and water were investigated. The TFs incorporation at 9 mg/g had the smallest droplet size and the highest G′ and G″ values. After storage for 21 days and thermal treatment at 105 °C for 4 h, the TFs retention in emulsions (9 mg/g) were 1.2-fold and 1.4-fold higher than aqueous solution, respectively, which might be attributed to the encapsulation of TFs in water droplets. During digestion, TFs emulsions provided a greater surface area for lipid digestion and led to a higher release of free fatty acids than emulsions without TFs. Moreover, there was sustained release of TFs in the emulsion, resulting in significantly enhanced TFs bioaccessibility (57.8 ± 9.2%) compared with aqueous solution (17.7 ± 1.1%) and Oil-Water mixture (32.6 ± 2.3%) after intestinal digestion. This study provides insights for food industry in designing W/O emulsion systems for the delivery of hydrophilic bioactive components.