Analytically pure C60 H18 is obtained by a Ru3 cluster complexation and decomplexation method. The crystal structure of C60 H18 consists of one flattened hemisphere, to which all 18 hydrogen atoms are symmetrically bonded, and one curved hemisphere akin to C60 . A benzenoid ring in the flattened hemisphere is isolated from the residual π systems by a belt composed of sp(3) -hybridized CH units. The average out-of-plane distances for carbon atoms attached to the benzenoid ring (0.14 Å) is substantially larger than that found in C60 F18 (0.06 Å). Several long C(sp(3) )C(sp(3) ) single bond lengths [1.61(3)-1.65(3) Å] are observed for C60 H18 . The reaction of [Ru3 (CO)12 ] and C60 H18 produces [Ru3 (CO)9 (μ3 -η(2) ,η(2) ,η(2) -C60 H18 )] (1), where the Ru3 triangle is regiospecifically linked to the hexagon opposite to the benzenoid ring. Compound 1 is the first transition metal complex of a polyhydrofullerene (fullerane). C60 H18 and 1 have been characterized by (1) H and (13) C NMR, UV/Vis, and mass spectroscopies. The HOMO-LUMO gap of C60 H18 is evaluated to be 1.51 V by cyclic voltammetry.