A new method of qualitative and quantitative determination of barbiturates in the pharmaceuticals by means of $alpha$-picoline-copper (II) was studied. Barbiturates in the pharmaceuticals were dissolved in the mixed solvent of 33% $alpha$-picoline-Carbontetrachloride to yield Complex Compounds of barbiturates-copper (II)-$alpha$-picoline. Complex Compounds of barbiturates show uniformly maximum absorption at the wavelength of 540m.mu. and wre to be identified at the concentration of 1 X 10$^{-4}$ Mole, and also was to be quantitatively determined at the concentration of 1 X 10$^{-3}$ Mole. By this method barbiturates in the pharmaceuticals could be determined in the presence of various compounds such as sulpyrine, isopropylantipyrine, antipyrine, phenacetin and etc. But Barbiturates could be also determined by this method after seperation with aminopyrine, acetaminophen, acetylsalicylic acid and etc. by column chromatography. And barbiturates and acetylsalicylic acid could be also determined by simultaneous equation while their complex compounds show uniformly each maximum absorption at the Wavelength of 540 m${mu}$ and 620 m${mu}$. I.R. spectra of these complex compounds show identification of Barbiturates derivatives. The composition ratio of these complex compounds were : barbiturates : Cu : ${alpha}$-picoline=2:1:2.