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A calix[3]carbazole-based cavitand was conveniently synthesized. It was found that the cavitand with adjustable conformation could show excellent complexation with fullerenes C60 and C70 in both solution and the solid state. Moreover, the crystal structures of the host–guest complexes show that the cavitand can stack into channel-like architectures, in which fullerenes are orderly arranged inside. [ABSTRACT FROM AUTHOR]