Summary Bambara groundnut is an underutilised African leguminous crop. This study investigated the effect of annealing on the complexing ability and functionality of Bambara groundnut starch with palmitic acid. Corn starch was included as the reference. Annealing created cracks and pores on the surface of Bambara groundnut and corn starches, respectively. Bambara groundnut starch had significantly higher amylose content, higher peak and final viscosities than corn starch. The peak viscosities of native Bambara groundnut and corn starches significantly reduced with palmitic acid addition. Greater reduction in peak viscosities was observed when the annealed starches were complexed with palmitic acid, suggesting that more palmitic acid was complexed after annealing. This was confirmed by XRD peaks and melting enthalpies. Pasting of native Bambara groundnut and corn starches with palmitic acid resulted in the formation of type I V‐amylose complexes, while type II complexes were formed from annealed starches pasted with palmitic acid.