The approach of combining enzymatic and transition-metal catalysis has been focused almost exclusively on using purified, isolated enzymes. The use of whole-cell biocatalysis, instead of isolated enzymes, with transition-metal catalysis, however, has been investigated only sparsely to date. Herein we present the development of two transition-metal catalyzed reactions used to derivatize styrene obtained from whole-cell biosynthesis. Using a biocompatible ruthenium cross-metathesis catalyst up to 1.5 mM stilbene could be obtained in the presence of E. coli, which simultaneously produced styrene. Using palladium catalysts and arylboronic acids, titers of up to 1 mM of several stilbene derivatives were obtained. These two transition-metal catalyzed reactions are valuable additions to the toolbox of combined whole-cell biocatalysis and transition-metal catalysis, offering the possibility to supplement biosynthetic pathways with the chemical versatility of abiological transition-metal catalysis.