AbstractOn the way to the fullerene‐acetylene hybrid carbon allotropes 2 and 6, the oxidative homocoupling of the 2‐functionalized 1‐ethynylated C60 derivatives 11, 12, 14, and 15 was investigated. Under Glaser‐Hay conditions, the two soluble dumbbell‐shaped bisfullerenes 17 and 18, with two C60 moieties linked by a buta‐1,3‐diynediyl bridge, were formed in 52 and 82% yield, respectively (Scheme 2). Cyclic‐voltammetric measurements revealed that there is no significant electronic communication between the two fullerene spheres via the buta‐1,3‐diynediyl linker. Removal of the 3,4,5,6‐tetrahydro‐2H‐pyran‐2‐yl (Thp) protecting groups in 18 gave in 80% yield the highly insoluble dumbbell 19 with methanol groups in the 2,2′‐positions of the buta‐1,3‐diynediyl‐bridged carbon spheres. Attempted conversion of 19 to the all‐carbon dianion 6 (C) via base‐induced elimination of formaldehyde was not successful presumably due to exo‐dig cyclization of the formed alkoxides. The occurrence of this cyclization under furan formation was proven for 2‐[4‐(trimethylsilyl)buta‐1,3‐diyn‐1‐yl][60]fullerene‐1‐methanol (21), a soluble model compound for 19 (Scheme 3). To compare the properties of ethynylated fullerene mono‐adducts to those of corresponding higher adducts, hexakis‐adducts 26 and 28 with an octahedral functionalization pattern resulting from all‐e (equatorial) additions were prepared by the reversible‐template method of Hirsch (Scheme 4). Reaction of the ethynylated mono‐adducts 25 or 13 with diethyl 2‐bromomalonate/1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in the presence of 1,9‐dimethylanthracene (DMA) as reversible template led to 26 and 28 in 28 and 22% yield, respectively. Preliminary experiments indicated a significant change in reactivity and NMR spectral properties of the fullerene addends with increasing degree of functionalization.