A photochromic dithienylethene-annulated N-heterocyclic carbene (NHC) Rh(I) complex was synthesized and found to undergo reversible electrocyclic ring closure upon alternate exposure to UV (lambda(irr) 313 nm) and visible (lambda(irr) >500 nm) radiation. Under ambient light, the Rh catalyst efficiently promoted the hydroboration of alkenes and alkynes with pinacolborane. However, upon IN irradiation to effect a photocyclization within the NHC ligand, the catalytic activity was reduced by up to an order of magnitude. The disparity in the rates was used to photoswitch the rates of a series of hydroboration reactions, thus demonstrating the first examples of photomodulating a transition-metal catalyst by tuning its electronic properties. The rate attenuation observed under UV irradiation was attributed to inhibition of the rate-determining reductive elimination step arising from a decrease in electron-donating ability of the photocyclized NHC ligated to the Rh center.