Here we report the synthesis of new mesoporous crystalline fullerene (C₇₀) cubes (MCFCs) at a liquid–liquid interface between tert-butyl alcohol (TBA) and a solution of C₇₀ in mesitylene under mild heat treatment. The highly crystalline pore walls of the MCFCs result in enhanced electrochemical and photoluminescence properties, which differ from pristine C₇₀ and crystalline C₇₀ cubes lacking mesopores.