Pyrolysis of cellulose with different catalysts has been conducted in a fixed-bed reactor. Micro-mesoporous composite molecular sieves of ZSM-5(38)/Al-MCM-41 with different Si/Al ratios were prepared under hydrothermal conditions. With powder X-ray diffraction (XRD), the catalyst samples were characterized. GC-MS was used to analyze the bio-oil composition. The effects of catalysts on the pyrolysis product yields were investigated and the results were compared with the results of experiments performed without catalyst under the same pyrolitic conditions. The presence of the catalysts decreased the liquid yield, while increased the moisture content. The major improvement in the quality of bio-oil with the use of catalysts was the increase of DL-2,3-Butanediol. ZSM-5(38)/Al-MCM-41(20) favored the formation of phenol and 2-methoxy-phenol. In addition, these catalysts were all benefit for the generation of small molecular compounds. Also, it was found that ZSM-5(38) was better for the production of C4?C5 compounds. And micro-mesoporous composite molecular sieves mainly promoted the production of C6?C8 compounds.