Ultraviolet emission from the OH(A-X) transition near 307 nm has been measured in a shock-tube for T = 1050-1400 K and P approximate to 1.2 atm. Experimental mixtures of H-2/SiH4/O-2/Ar and kinetics calculations were used to identify the elementary reaction forming electronically excited OH (OH*) in a Si-containing environment and directly measure its absolute rate coefficient. The primary Si-containing reaction found to form OH* is SiH + O-2 = OH* + SiO with a rate expression of k(0) = 1.5 x 10(7) exp(+16.4 kcal/RT) +/- 2.3 x 10(10) cm(3) mol(-1) s(-1) This work provides insights into the mechanisms of combustion processes involving silicon. (c) 2006 Elsevier B.V. All rights reserved.