Determination of chloride ion in concentrated NaOH solution by capillary electrophoresis has been studied. The analysis was performed by indirect UV absorption detection using chromate buffer at 254nm. The matrix effect of the sample has been observed so that the sensitivity in strong NaOH solutaion has decreased up to 10% of that in distilled water. The pH effect of the sample on the sensitivity of CE peaks has been investigated. The method for increasing the sensitivity have been investigated and the optimum pH and concentration of the buffer were 7.5 and 10mM, respectively. A cationic surfactant cetyltrimethylammonium bromide(CTAB), was added to a buffer solution in order to reverse the electroosmotic flow(EOF) in the capillary. This results in a short analysis time and better peak shapes. Using this optimum condition, the determination of chloride ion in real environmental sample has been performed, which is captured in strong NaOH absorbent prepared for absorbing gas from chimney. The standard addition method has been applied for the quantitative analysis, and it was obtained the good reproducibility.