Indole aziridines and their hydroxyl derivatives have been used for the preparation of a small library ofnovel functionalized bisindoles. Diversification of these building blocks by solvent-free C−C-bondformation on solid support yielded annulated Hymenialdisine analogues under mild reaction conditions.Indoles as C-nucleophiles form potentially pharmacologically active bisindoles through an electrophilicaromatic substitution pathway in good to excellent yields. Further transformations of the indole aziridineswith H-, N-, and O-nucleophiles demonstrate their versatility as key intermediates in diversity orientedsynthesis. The hydroxyl precursor leads also to unsymmetrical bisindoles under similar reaction conditions.Important intermediates and final library compounds were confirmed by X-ray analysis. Theoretical studieson these systems show the possible cationic intermediate in the substitution pathway.