The effects of different surfactants (sodium 2-ethylhexyl sulfate, sodium decyl sulfate, sodium dodecyl sulfate and sodium tetradecyl sulfate) on the analysis of phenolic compounds by microchip-CE with pulsed amperometric detection were investigated. Using sodium decyl sulfate as a model surfactant, the effects of concentration and pH were examined. Under the optimized conditions, the analysis of six phenolic compounds was performed and compared with control runs performed without surfactant. When these surfactants were present in the run buffer, decreases in the migration time and increases in the run-to-run reproducibility were observed. Systematic improvements in the electrochemical response for the phenolic compounds were also obtained. According to the results presented, surfactants enhance the analyte–electrode interaction and facilitate the electron transfer process. These results should allow a more rational selection of the surfactants based on their electrophoretic and electrochemical effects.