Ferrocenyl-substituted bicyclo[1.1.1]pentasilanes 1, 2, and 3 were synthesized by the reactions of bromo-substituted bicyclo[1.1.1]pentasilanes with lithioferrocene. Significant interactions between bicyclo[1.1.1]pentasilane and ferrocenyl units were suggested by cyclic voltammetry, UV-vis absorption spectrum, and theoretical calculations.