The species concentrations of non-premixed hydrogen and syngas flames were examined using results obtained from direct numerical simulation technique with flamelet generated manifold chemistry. Flames with pure H2 and H2/CO mixtures are discussed for an impinging jet flame configuration. Single-point data analyses are presented illustrating the effects of fuel composition on species concentrations. In general, scatterplots of all species show the effects of fuel variability on the flame compositional structures. The behaviours of major combustion products and key radicals species indicate the effects of CO concentration on the 2/CO syngas combustion. In particular, high concentration of CO tends to induce local extinction in the 2/CO flames in which critical chemical reactions of the fuel mixture such as CO + OH become important. The unsteady fluctuations of species profiles in the wall jet region characterise the complexity of the distributions of compositional structures in the near-wall region with respect to the effects of CO concentration on the combustion of hydrogen-enriched fuels.