β-Carotene microcapsules of high loading (>10%, w/w) usually suffered from poor physicochemical stability and low bioaccessibility. Herein, polyphenols with different polarities were co-milled with β-carotene to relieve aforementioned obstacles. The results indicated that different interplays between β-carotene and polyphenols were induced during co-milling owing to distinct polarities and locations of polyphenols in the microcapsules. Specifically, β-carotene microcapsules incorporating epigallocatechin gallate (EGCG) exhibited lower particle size after rehydration (334.1 nm) and higher encapsulation efficiency (98.75%). The highest retention rates of β-carotene (55 °C for 40 d) in both powdery microcapsules (76.03%) and rehydrated suspensions (41.31%) were achieved in the presence of tea polyphenol palmitate (TPP). Curcumin (Cur) exhibited the best efficacy in boosting the bioaccessibility of β-carotene (9.34%) due to its efficacy in accelerating the permeation of solubilized β-carotene into the micellar phase. Furthermore, the physical properties of β-carotene microcapsule-fortified tablets were also appraised and zein was crucial in regulating the release kinetics of β-carotene in the microcapsules from tablets.