Simple, mild, and efficient conditions are reported for a Pd(0)-catalyzed Heck reaction that delivers high yields and selectivity for (E)-styrenyl products using electronically nonbiased olefin substrates bearing a range of useful functionality. Preliminary mechanistic studies demonstrate that the sigma-donating DMA solvent is crucial for high selectivity. Further studies suggest that the catalyst distinguishes between beta-hydrogens on the basis of their relative hydridic character, in contrast to previously reported Pd(II)-catalyzed oxidative reaction conditions.