Novel Pickering emulsions were stabilized by complex interfaces in the presence of zein colloidal particles (ZCPs), propylene glycol alginate (PGA), and rhamnolipid (Rha) for delivery of β-carotene. The influence of the particle-surfactant, particle-biopolymer, and particle-biopolymer-surfactant mixed interfaces on the physiochemical properties and digestion fate of Pickering emulsions was investigated. It is the first time that three different types of emulsifiers have been used to synergistically stabilize food Pickering emulsions for delivery of lipophilic nutraceuticals. The physicochemical stability, microstructure, rheological properties, and in vitro gastrointestinal digestion of Pickering emulsions were controlled by the addition sequence and mass ratio of multiple stabilizers, which showed the enhanced stability and delayed lipid digestion of the particle-biopolymer-surfactant-stabilized Pickering emulsions. After encapsulation into Pickering emulsions, the retention rate of β-carotene increased 2-fold under UV radiation for 8 h. The coexistence of ZCPs, PGA, and Rha could induce the competitive displacement, multilayer deposition, and interparticle network at the interface. The combination of particles, a biopolymer, and a surfactant delayed the lipolysis during in vitro gastrointestinal tract. By modulating the interfacial composition, the release rate of free fatty acids from Pickering emulsions was reduced from 19.46% to 2.83% through different mechanisms. The novel Pickering emulsion could be incorporated in foods as well as pharmaceuticals for controlled lipid digestion or targeted nutrient delivery purposes.