Tri-cavity hosts consisting of one pillar[5]arene (P5) sandwiched by two β-cyclodextrins (CDs) were synthesized, and their diastereoseparation was successfully accomplished. Photocyclodimerization of 2-anthracenecarboxylate with these hybrid hosts demonstrated the critical dependence of stereoselectivity on the absolute configuration of the central P5 and the conjugating positions on the β-CD, and gave the non-classical HT photodimers in up to 87% ee.