An experimental investigation of entrainment and mixing in reacting and non-reacting turbulent mixing layers at large Schmidt number is presented. In non-reacting cases, a passive scalar is used to measure the probability density function (p.d.f.) of the composition field. Chemically reacting experiments employ a diffusion-limited acid-base reaction to directly measure the extent of molecular mixing. The measurements make use of laser-induced fluorescence diagnostics and high-speed, real-time digital image-acquisition techniques. Our results show that the vortical structures in the mixing layer initially roll-up with a large excess of fluid from the high-speed stream entrapped in the cores. During the mixing transition, not only does the amount of mixed fluid increase, but its composition also changes. It is found that the range of compositions of the mixed fluid, above the mixing transition and also throughout the transition region, is essentially uniform across the entire transverse extent of the layer. Our measurements indicate that the probability of finding unmixed fluid in the centre of the layer, above the mixing transition, can be as high as 0.45. In addition, the mean concentration of mixed fluid across the layer is found to be approximately constant at a value corresponding to the entrainment ratio. Comparisons with gas-phase data show that the normalized amount of chemical product formed in the liquid layer, at high Reynolds number, is 50% less than the corresponding quantity measured in the gas-phase ease. We therefore conclude that Schmidt number plays a role in turbulent mixing of high-Reynolds-number flows.