Bicyclo[10.10.10]dotriacontanes, the largest bicyclo[n.n.n]-alkanes ever known, have been first synthesized by Raney nickel reduction of trithienyltmethanophanes consisiting of two tris(2-thienyl)methanes and three etheno bridges. X-ray crystallographic analysis of a crystalline derivative confirmed the structure, though disorder of included hexane molecules lowered the accuracy.