The stereocontrolled synthesis of (E)-configured styrenes via Pd(0)-catalyzed cross-couping of (E)-alkenylgermanes with aryl bromides is described. The germanes employed have bis(naphthalen-2-ylmethyl) substitution to allow photooxidative activation toward coupling and a C 8 F 17 -fluorous tag to facilitate purification by fluorous solid-phase extraction (F-SPE). The selectivities obtained suggest that a germyl-Stille rather than Heck-type mechanism predominates in the coupling step.Biaryls and styrenes are key structural motifs in numerous bioactive natural products, pharmaceuticals, agrochemicals, dyes, organic semiconductors, and ligands/auxiliaries for asymmetric synthesis. 1 We recently described a new method for the preparation of biaryls via the Pd(0)-catalyzed germylStille cross-coupling of light fluorous-tagged arylgermanes with aryl bromides following photochemical activation of the "safetycatch" arylgermane partner (Scheme 1).2,3