CuCl has been investigated with regard to its catalytic effects on pyrolysis of five biomass species, i.e., two kinds of typical forest waste (bamboo and fir wood), cellulose, xylan, and lignin by thermal analysis experiments. It shows that, with the presence of CuCl catalyst, the pyrolysis peaks shift to a lower temperature than those of a pure sample, and the maximum weight loss rate of two kinds of typical forest wastes was increased. The CuCl catalysis can also increase the amount of char residue. The activation energy and frequency factor of pyrolysis reaction for all samples were obtained by kinetic methods of analysis, the value of E and A of the mixture were higher than those of the sample (except lignin) in the absence of catalyst.