α,β‐Unsaturated acylimidazoles have been used in a plethora of enantioselective transformations over the years and have unsurprisingly become privileged building blocks for asymmetric catalysis. Interestingly however, their use in asymmetric biohybrid catalysis as bidentate substrates able to interact with artificial metalloenzymes has only recently emerged, expanding considerably in the last few years. Easy to prepare and to post‐transform, α,β‐unsaturated acylimidazoles appear as leading synthons for the asymmetric construction of C−C and C−O bonds. This Minireview highlights the current and increasing interest of these key building blocks in the context of asymmetric biohybrid catalysis with the aim to stimulate further research into their still unexploited potential.