The first implementation of a combined laser absorption diagnostic/gas chromatography (GC) sampling system for the measurement of combustion-relevant species in a conventional shock tube configuration is reported, with ethylene pyrolysis as an example application. A heated, endwall sampling system is used to extract a post-shock sample for GC analysis. Analysis of the gas sample yields a measurement of the ultimate mole fraction values of multiple species (currently ethylene, acetylene, hydrogen, and methane) at the end of the reflected shock test time. A 10.532-nm laser absorption diagnostic is simultaneously used to measure time-resolved ethylene. A method to accurately model sampled speciation results using published kinetic models is discussed. A method for extending laser measurements into the expansion fan region for direct comparison with sampled GC results has also been developed. The combined optical and sampled-gas measurement techniques were used to study ethylene pyrolysis (1.0% mole fraction ethylene/argon) at approximately 5 atm, over a range of temperatures (1200-2000 K). The ethylene mole fraction measurements obtained using both techniques show close agreement. (C) 2018 The Combustion Institute. Published by Elsevier Inc. All rights reserved.