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A multicomponent tandem arylation reaction was established under transition‐metal‐free conditions to synthesize structurally diverse imidazo[1,2‐a]pyridines. As N,N‐dimethylaniline is not only a reactant but also a methylation reagent, its use affords an alternative route for methylation. This approach features mild reaction conditions and good functional group tolerance, providing 29 compounds in acceptable yields. [ABSTRACT FROM AUTHOR]