The reaction of 4‐vinylpyridine (4‐VP) with acylating agents in diethyl ether was investigated. Acetyl chloride (AcCl) and trifluoroacetic anhydride [(TFAc)2O] yield colored oligomers with 4‐VP, denoted P‐4VP—AcCl (III) and P‐4VP—(TFAc)2O (IV). Nuclear magnetic resonance spectrometry was used to analyze these products. A structure (XII), representing a random copolymer resulting from 1,2‐polyaddition and 1,6‐polyaddition to 4‐VP, is proposed for III and IV. Alternative mechanisms which explain these observations are discussed. Acetic anhydride (Ac2O) does not acylate 4‐VP. It is proposed that this result is caused by the inability of Ac2O to quaternize 4‐VP as an initial step leading to polymerization.