We present the first analysis of performance of hydroxamate linkers as compared to carboxylate and phosphonate groups when anchoring ruthenium-polypyriclyl dyes to TiO2 surfaces in dye-sensitized solar cells (DSSCs). The study provides fundamental insight into structure/function relationships that are critical for cell performance. Our DSSCs have been produced by using newly synthesized dye molecules and characterized by combining measurements and simulations of experimental current density-voltage (J-V) characteristic curves. We show that the choice of anchoring group has a direct effect on the overall sunlight-to-electricity conversion efficiency (eta), with hydroxamate anchors showing the best performance. Solar cells based on the pyridyl-hydroxamate complex exhibit higher efficiency since they suppress electron transfer from the photoanode to the electrolyte and have superior photoinjection characteristics. These findings suggest that hydroxamate anchoring groups should particularly valuable in DSSCs and photocatalytic applications based on molecular adsorbates covalently bound to semiconductor surfaces In contrast, analogous acetylacetonate anchors might undergo decomposition under similar conditions suggesting limited potential in future applications.