We report a general emulsion soft-template method to synthesize porous graphene foams for multi-functional applications, including lithium–oxygen batteries and oil-adsorption. Multiple micro-emulsions and micelles were employed to produce three-dimensional porous graphene with well-tailored inter-architecture for the first time. Detailed mechanism study reveals that specific interfacial interactions, such as π–π interaction, hydrophobic affinity or electrostatic interaction, are vital for the formation of porous graphene materials. When applied as cathode materials in lithium–oxygen batteries, the porous graphene foams exhibited good catalytic activity. Besides, the porous graphene materials also demonstrated the capability for oil adsorption with a high efficiency.