The self-assembly of styrene-type olefins into the corresponding stilbenes was conveniently performed in the Deep Eutectic Solvent ( DES ) mixture 1 ChCl /2 Gly under air and in the absence of hazardous organic co-solvents using a one-pot chemo-biocatalytic route. Here, an enzymatic decarboxylation of p -hydroxycinnamic acids sequentially followed by a ruthenium-catalyzed metathesis of olefins has been investigated in DES . Moreover, and to extend the design of chemoenzymatic processes in DESs , we also coupled the aforementioned enzymatic decarboxylation reaction to now concomitant Pd-catalyzed Heck-type C-C coupling to produce biaryl derivatives under environmentally friendly reaction conditions., (Copyright © 2020 Ríos-Lombardía, Rodríguez-Álvarez, Morís, Kourist, Comino, López-Gallego, González-Sabín and García-Álvarez.)