An expedient access to a series of nonsymmetrical bis(indolyl)methanes (BIMs) through transindolylation of readily available symmetrical 3,3′-BIMs with various indoles catalyzed by silica-supported sulfuric acid has been established. This approach not only provides a useful strategy for the synthesis of structurally diverse BIMs, but also provides examples of nucleophilic substitution of BIMs with aromatic and nonaromatic π-systems, leading to a library of indolyl-substituted tri- and diarylmethanes. Moreover, this method was successfully applied in the first total synthesis of the 2,3′-BIM alkaloid (±)-colletotryptin E in three steps with an overall yield of 46%. The features of this procedure include a metal-free process, an inexpensive and environmentally friendly catalyst, mild reaction conditions, broad functional-group tolerance, good yields, and gram-scalable preparations.