A cobalt(III)-catalyzed coupling of substituted acrylamides with maleimides in the presence of 30 mol% pivalic acid providing olefin-migrated succinimide derivatives in a redox-neutral manner is described. The coupling reaction was examined with various substituted acrylamides and maleimides. The scope of the C–H alkylation reaction was also examined with substituted acrylates. A possible reaction mechanism involving a five-membered cobaltocycle as a key intermediate is proposed.