Abstract The triad distributions of 1,1‐diphenylethylene (D)–methyl acrylate (M) copolymers have been determined from NMR measurements and examined according to the terminal and penultimate models of copolymerization theory. As expected from the diamagnetic shielding by the phenyl rings of the nearest D units, the methoxy proton resonances were found to appear as three resolved peaks at 6.4–6.6 τ, 6.7–7.0 τ, and 7.2 τ, and have been assigned to the central M units of the triads MMM, MMD or DMM and DMD, respectively. The copolymer composition and the triad distributions observed are shown to agree better with the terminal model with the methyl acrylate reactivity ratio of 0.092 ± 0.010 than with the penultimate model.