Hydrogen from solid wastes is produced by pyrolysis. In this study, cotton cocoon shell samples were subjected to direct and catalytic pyrolysis to obtain hydrogen rich gaseous products at desired temperatures. The samples, both untreated and impregnated with catalyst, were pyrolyzed at 775, 850, 925, 975 and 1025 K temperatures. The total volume and the yield of gas from both pyrolyses increase with increasing temperature. The largest hydrogen rich gas yield obtained from cotton cocoon shell, using about 13% ZnCl2 as catalyst at about 1025 K temperature, is 59.9%. In general, in the pyrolysis of cotton cocoon shell, the yield of hydrogen rich gaseous product increases with ZnCl2 catalyst, but the yield of pyrolytic gas decreases in spite of increasing the yield of charcoal and liquid products. The catalytic effect of Na2CO3 was greater than that of K2CO3 for the cotton cocoon shell, especially in low temperature pyrolysis runs.