The critical examination of the spectrophotometric method for determining microgram quantities of phosphate by the n-butyl acetate extraction as molybdophosphoric acid and subsequent development of the molybdenum blue has been made. In this procedure from 2 to 8 ${mu}g$. of phosphate-phosphorus can be determined under optimum conditions. The final concentration of ammonium molybdate and the final acidity of perchloric acid for the formation of heteropoly acid are suitable to be ranges of 0.5 to 1.1% and 0. 5 to 1. 1 N respectively, and subsequently extracted with 10 ml. of n-butyl acetate. The extract is developed to molybdenum blue with 5.0 ml. of 1. 3% stannous chloride in 1N hydrochloric acid. The color is stable for at least one hour in the use of perchloric acid for the condensation. In order to determination of submicrogram amounts of phosphate, the sensitivity of the molybdenum blue method is hardly sufficient, a sensitive and stable molybdenum(V)-thiocyanate complex method has been investigated. By the procedure less than 1.2 ${mu}g$. of phosphate-phosphorus can be determined with an accuracy of less than 5% the relative error. The molybdenum(Ⅵ) extracted by the above procedure is reduced to molybdenum(V) in the extract directly with a solution of 4 to 10% of stannous chloride, 0.5 to 1.5 mM of copper, and 0.1 to 0.9 N of perchloric acid as final concentration in 4.3 to 6.3 N of hydrochloric acid or 9.0 to 13.0 N of sulfuric acid by heating for one minute in boiling water, after cooling, the molybdenum(V)-thiocyanate complex color is developed by adding 6.0 M ammonium thiocyanate solution making the final concentration to be in a range of 0.4 to 0.9 M. This procedure the very sensitive, reliable, and stable can be applied to determining submicrogram amounts of phosphate in natural waters with a precision of 1.6 ${ imes};10^{-2}$ the standard deviation as absorbance.