We have measured, for the first time, subshell-resolved L - K ( - K, - K and - K) electron transfer cross sections for electron transfer from the L-shell of the target to the vacant K-shell of the projectile. These cross sections are derived by measuring the charge-state dependence of the target L x-rays from a thin Au target using bare and H-like sulphur ions. In addition, the subshell-resolved ionization cross sections are also derived from the analysis of the L x-ray production cross sections. We found that the vacancy production cross section for the subshell is much smaller than that for strongly bound subshell and the - K transfer cross section is also much smaller than the - K transfer cross section. These observations are contrary to the prediction of first-order theories.