The field of biocatalysis is expanding owing to the increasing demand for efficient low-cost green chemical processes. However, a feasible strategy for achieving product separation, enzyme recovery, and high catalytic efficiency in biocatalysis remains elusive. Herein, we present thermoresponsive Pickering high internal phase emulsions (HIPEs) as controllable scaffolds for efficient biocatalysis; these HIPEs demonstrate a transition between emulsification and demulsification depending on temperature. Ultra-high-surface-area Pickering HIPEs were stabilized by Candida antarctica lipase B immobilized on starch particles modified with butyl glycidyl ether and glycidyl trimethyl ammonium chloride, thus simplifying the separation and reuse processes and significantly improving the catalytic efficiency. In addition, the switching temperature can be precisely tuned by adjusting the degree of substitution of the modified starches to meet the temperature demands of various enzymes. We believe that this system provides a green platform for various interfacial biocatalytic processes of industrial interest.