The direct utilization of amines for C-C bond formation without prefunctionalization remains a significant challenge. Herein, we report the base-promoted deaminative coupling of gramines with aminomalaimides under redox-neutral conditions. In this operationally simple reaction, a series of indolmethyl-substituted aminomaleimides that emitted fluorescence were synthesized in good-to-excellent yields. Biological evaluation revealed that some products exhibited antiproliferative activity against human cancer cell lines.