Capillary electrochromatography (CEC) using fibrous cellulose acetate (CA) stationary phase was investigated. The advantage of this fiber-packed column is relatively easy preparation process compared with other conventional CEC columns, such as particle-packed and wall-coated capillaries. CA fibers are manually packed into a capillary with two guide liners and fixed with a frit at the column inlet. The separation characteristics of this column were investigated using n-alkyl p-hydroxybenzoates (parabens) as the sample probe. It has been demonstrated that the use of a short column length and a specially designed tee-connector as the injection device should make the separation performance and efficiency much higher on the fiber-packed columns. Sufficient separation between methyl and n-butylparabens is obtained on the 5-cm-packed column and linear relationships between the injection time and the peak area are observed. Bubble formation is not encountered during the analysis.