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A kind of copolymer, poly(4‐vinylsulfonylaniline‐co‐acrylamide) (P(VSA‐co‐AM)), was synthesized by the copolymerization of 4‐vinylsulfonyl aniline (VSA) and acrylamide (AM) using tetrahydrofuran (THF) as the solvent and 2,2′‐azobis(2‐methylpropionitrile) (AIBN) as the initiator in the presence of a total monomer mass concentration of 15%, and a polymerization duration of 10 h. The effect of the monomer feed ratio on the copolymerization is investigated, and the results reveal that increasing the content of VSA in the monomer feed ratio increases the proportion of VSA in the copolymer. A feed ratio of 5:5 is selected for the copolymerization of VSA and AM, and a copolymer with 28% VSA is obtained. After diazotization, P(VSA‐co‐AM) with a molecular weight of 4.45 × 103 and a VSA ratio of 28% is coupled with the coupling component containing more chloro‐s‐triazine reactive groups, thus resulting in macromolecular reactive dyes. The fixation of the obtained macromolecular reactive dyes A, B, and C on cotton fabric is over 93% and have good light, rubbing, and washing fastnesses, thus indicating their potential application in the dyeing of cotton fabric.

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