The Heck reaction has been used to couple olefins to a Si(111) surface that was functionalized with a mixed monolayer comprised of methyl and thienyl groups. The coupling method maintained a conjugated linkage between the surface and the olefinic surface functionality, to allow for facile charge transfer from the silicon surface. While a Si(111) surface terminated only with thienyl groups displayed a surface recombination velocity, S, of 670 ± 190 cm s–1, the mixed CH3/SC4H3–Si(111) surfaces with a coverage of θSC4H3 = 0.15 ± 0.02 displayed a substantially lower value of S = 27 ± 9 cm s–1. Accordingly, CH3/SC4H3–Si(111) surfaces were brominated with N-bromosuccinimide, to produce mixed CH3/SC4H2Br–Si(111) surfaces with coverages of θBr–Si < 0.05. The resulting aryl halide surfaces were activated using [Pd(PPh3)4] as a catalyst. After activation, Pd(II) was selectively coordinated by oxidative addition to the surface-bound aryl halide. The olefinic substrates 4-fluorostyrene, vinylferrocene, and protoporphyrin IX dimethyl ester were then coupled (in dimethylformamide at 100 °C) to the Pd-containing functionalized Si surfaces. The porphyrin-modified surface was then metalated with Co, Cu, or Zn. The vinylferrocene-modified Si(111) surface showed a linear dependence of the peak current on scan rate in cyclic voltammetry, indicating that facile electron transfer had been maintained and providing evidence of a robust linkage between the Si surface and the tethered ferrocene. The final Heck-coupled surface exhibited S = 70 cm s–1, indicating that high-quality surfaces could be produced by this multistep synthetic approach for tethering small molecules to silicon photoelectrodes.