Different rare earth(RE=La, Ce, Pr, Nd, Sm, Y) and Cu modified nickel catalysts for hydrogen production from methane decomposition were synthesized by a sol-gel process and method. The catalysts were characterized or analyzed through Brumauer-Emmett-Teller(BET), X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM) techniques. And the hydrogen production performance was also evaluated by a fixed-bed and micro-reaction technique with CH4→C+H2 as a probe reaction. The results showed that rare earth modification had played a great role for nickel catalysts, for example, smaller nickel particles, good thermal stability, high activity, etc. La was the best additive among rare earth modification. The SEM of rare earth modified catalysts showed ordered flower-like structure and rare earth modification made the nickel particles move to the surface of catalysts. In addition, the SEM of nano-carbons was also changed by rare earth modification with long, narrow nano-carbon fibers or tubes obtained. Solid carbon formation was prevented by rare earth modification. The catalysts were characterized or analyzed through Brumauer-Emmett (RE = La, Ce, Pr, Nd, Sm, Y) and Cu modified nickel catalysts for hydrogen production from methane decomposition were synthesized by a sol-gel process and method. -Teller (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) techniques. And the hydrogen production performance was also evaluated by a fixed-bed and micro- reaction technique with CH4 → C + H2 as a probe reaction. The results showed that rare earth modification had played a great role for nickel catalysts, for example, smaller nickel particles, good thermal stability, high activity, etc. La was the best additive among rare earth modifications. The SEM of rare earth modified catalysts showed ordered flower-like structure and rare earth modification made of nickel particles move to the surface of catalysts. In addition, the SEM of nano-carbons was also changed by rare earth modification with lon g, narrow nano-carbon fibers or tubes obtained. Solid carbon formation was prevented by rare earth modification.