Due to special importance of hydrogen as a substance widely used in chemical industry and as pure ecological fuel, vast investigations dealing with its more economically profitable production have been performed recently. Literature review on actual study of researches connected with hydrogen production has revealed that hydrogen can be obtained using traditional methods like water electrolyses, water decomposition thermochemical cycles, photochemical water decomposition, as well as nontraditional ways like catalytic water radiolyses. In spite of the fact that significant progress has been made in this direction, the problem of searching more productive catalysts is still a burning one. The research targeted at stating optimal conditions for obtaining hydrogen via water radiolyses, using as catalytic agents the following heteronuclear coordination compounds: 1,2-[Co(NH3)4(NO2)2][Bi(Edta)(H2O)] (I) and [Cu(H2O)6][Bi(Edta)(H2O)]⋅2H2O (II). Water radiolytic decomposition has been performed at the Institute of Nuclear Investigations, Pitesti, Romania, using as radiation source 60 27 Co isotope with 5.104 Ci activity and that emits a debit dose of 8.5 KGy/h close to the respective samples. The quantity of the resulted products, as well as the one of the gases from the initially irradiated vessels, was determined using mass-spectrometry technique. It has been established that hydrogen radiolytic output, when (I) and (II) were used as catalysts, went 30-40 times up compared with non-catalytic water radiolysis and 1.3-2.0 times up when compared with the most effective catalysts described in the literature. The efficiency of the catalyst depends on complex cation nature and in this case compound (I) is more effective than (II). The discovered properties of the cation- anion heterometallic coordination compounds of Bismuth (III) with Co(III) and Cu(II), make a valuable contribution to hydrogen production technology. The investigations have been performed with financial support of National Project Nr. 45.003P.