The present disclosure relates to a porous liquid or a porous liquid enzyme system that includes a high surface area solid and a liquid film substantially covering the high surface area solid. The porous liquid or porous liquid enzyme may be contacted with a fluid that is immiscible with the liquid film such that a liquid-fluid interface is formed. The liquid film may facilitate mass transfer of a substance or substrate across the liquid-fluid interface. The present disclosure also provides methods of performing liquid-based extractions and enzymatic reactions utilizing the porous liquid or porous liquid enzyme of the present disclosure. The present disclosure also provides methods for selecting the components of the porous liquid or a porous liquid enzyme system and methods of self-replenishing the used liquid coating.