2D computer simulation revealed that amino acids and weak electrolytes were cationized because of the migration of counter-ion from a BGE zone to a sample zone, which encouraged electrokinetic injection (EKI) of these analytes (by the mobility-boost (MB) effect). To investigate the effects of kinds and concentrations of counter-ions on the MB effect and the analyte amount injected into the capillary, experiments, and 1D computer simulations were performed. When acetate was used as the counter-ion, the LODs (S/N = 3) of l-histidine and creatinine, respectively, reached 0.10 and 0.25 nM because of the concentration effect by transient ITP (tITP). The concentrations of l-histidine and creatinine in human blood plasma obtained using the proposed method were agreed with those obtained using the conventional methods. The proposed method can be applied to the analysis of amino acids and weak bases that have similar pI and pK(a) to l-histidine and creatinine.