The spectrophotometric determination of trace selenium(Ⅳ) using its catalytic reaction has been studied in aqueous solutions. The catalytic reaction of phenylhydrazine hydrochloride with selenium(Ⅳ) in an acidic aqueous medium produces benzenediazonium ion which will be converted into a red-coloured azo dye by coupling with H-acid(8-amino-1-naphtol-3,6-disulfonic acid disodium salt). For the reaction, the experimental conditions such as amounts of the reagents and pH of the sample solutions were optimized. After 15 ml of the sample solution was treated with 1 ml of 0.1 M EDTA solution to mask $Fe^{3+}$, etc., 1 ml of 0.06 M phenylhydrazine hydrochloride, 1 ml of 0.02 M H-acid, and 3 ml of 0.3 M-$KClO_3$ were added into the solution, sequentially. The solution was adjusted to pH 1.4 with HCl. After it was heated in a steam bath for 30 minutes, the solution was cooled down to a room temperature and then diluted to 25 ml with deionized distilled water. A blank solution for the absorbance measurement was prepared from the deionized water. The absorbance was measured at 527 nm. Using the above procedure, the trace amount of selenium was determined in natural waters such as tap, river and pond waters by a standard curve method and recoveries of Se spiked to samples were also obtained. From the recoveries of 104 to 111%, it could be concluded that this method was applicable to the quantitative determination of ng/ml level of selenium in natural waters.