The synthesis of aromatic amines is of continuous interest in chemistry. An exceptionally versatile three‐component reaction that directly transforms inexpensive nitro compounds, boronic acids, and trialkyl phosphites into tertiary aromatic amines has been realized. The reaction tolerates alkyl and aryl substituents on the nitro and boronic acid moieties, as well as functionalized phosphites. No transition‐metal catalysis is required. The method is orthogonal to other classical metal‐catalyzed syntheses since it tolerates the presence of halogens, and also permits the synthesis of functionalized compounds such as α‐amino ester derivatives.