The K-beta/K-alpha, X-ray intensity ratios of Co, Ni, Cu and Zn in metalophthalocyanines complexes have been studied. Co, Ni, Cu and Zn elements have been excited by using 59.5 keV photons emitted by 50 mCi (241) Am radioactive source. K X-rays emitted by samples have been counted by a Si(Li) detector with resolution 0.16 keV at 5.9 keV. We have found that K-beta/K-alpha X-ray intensity ratios of Co, Ni, Zn, and Cu complexes have changed depending on chemical structures of Co, Ni, Zn and Cu. The measured values have been compared with the theoretical predictions and experimental values of pure elements.