Abstract: | During studies on exploiting the catalytic promiscuity of crude porcine pancreas lipase (PPL) in ionic liquid for C?C bond formations, bovine serum albumin (BSA) was found to be competing for these reactions. After a detailed investigation, we establish that these transformations are possible by unspecific protein catalysis rather than catalytic promiscuity of “PPL” – a first insight into the role of protein impurities in crude enzyme. Thus, a novel and highly efficient, environmentally friendly approach involving synergistic catalysis by bovine serum albumin‐1‐butyl‐3‐methylimidazolium bromide (BSA‐bmim]Br) has been developed for the synthesis of (E)‐α,β‐unsaturated compounds including a one‐pot cascade synthesis of cinnamic acids and coumarins via aldol, Knoevenagel and Knoevenagel–Doebner condensations. |