Catalyzed thermal decomposition of methane to produce hydrogen was studied. The carbon microfibers with embedded Ni, Cu and Co metals and metal phosphides were introduced as the novel catalysts. The catalysts were prepared by needle-less electrospinning being a versatile method for fibers production in large scale. The efficiency of methane decomposition by utilization of micro fiber carbon supported metal catalysts was studied by the pyrolysis-capillary gas chromatography method. The experiment was carried out in the temperature range from 973.15 to 1073.15 K. Kinetic parameters were calculated based on the Demitcheli kinetic model. It was found that the morphology, schedule of heat treatment and type and content of incorporated transition metals and metal phosphides may be the controlling parameter in the catalytic decomposition of methane. The highest conversion rates about 54% were achieved using carbon microfibers doped with cobalt and cobalt phosphide nanoparticles. The catalyst was heat treated in argon atmosphere followed by the hydrogen reduction. The second highest conversion rates were achieved with carbon microfibers doped with nickel and nickel phosphide nanoparticles carbonized only under argon atmosphere. Graphic