The newly discovered cage-like borospherene D 2 d B 40 with two η 6 -B 6 hexagons and four η 7 -B 7 heptagons on the surface may serve as an effective multi-dentate ligand to coordinate transition metals. Based upon extensive density functional theory calculations, we present herein the possibility of the exohedral complex series (C 6 H 6 Cr) n &B 40 (n = 1–6) with n Cr centres sandwiched between the central η 6/7 -B 40 unit and n planar η 6 -C 6 H 6 ligands. C 6 H 6 Cr fragments in (C 6 H 6 Cr) n &B 40 occupy the η 6 -B 6 hexagonal coordination site atop the B 40 cage first, the four neighboring η 7 -B 7 heptagons on the waist next, and finally the η 6 -B 6 hexagon at the bottom, forming a multinuclear complex series effectively stabilized by n C 6 H 6 Cr fragments. The two η 6 -B 6 hexagons and four η 7 -B 7 heptagons on the spherical surface of B 40 can be practically viewed as six independent coordination sites to coordinate Cr centers with almost the same coordination energies. Detailed bonding analyses indicate that the eclipsed C 2 v C 6 H 6 Cr&B 40 ( 1 - 1 ) possesses a coordination bonding pattern similar to that of dibenzenechromium, with the B 40 ligand inheriting the σ + π double delocalization bonding pattern of the parent borospherene. The IR, Raman, and UV–vis absorption spectra of C 2 v C 6 H 6 Cr&B 40 ( 1 - 1 ) are theoretically simulated to facilitate its future experimental characterization.