Pyrolysis of sedimentary organic matter under inert atmosphere and by low-rate temperature programming produces solid and liquid pyrolyzates which have been studied by different techniques. The result is a good agreement between such pyrolyzates and samples having undergone natural maturation. For methane such a comparison is not possible, because of the mobility of methane in nature but, on the basis of previous studies, methane formation from different types of organic matter can be studied in the same conditions. The organic matter is studied as kerogen, outside and inside the original rock. No significant difference is seen in methane formation, which always occurs during the main stage of hydrocarbon formation or after it, but never before. The minimum temperature is 250°C. In order to test the likeliness of a catalytic effect, some kerogens are mixed with industrial catalysts and processed as usual. The distribution of hydrocarbons is thereby modified, the temperature of formation of hydrocarbons is lowered by circa 50°C, but the formation of methane is not modified. Thermal cracking mechanisms explain quite well the formation of hydrocarbons and methane as it occurs in our experiment. Catalysts, though inducing other mechanisms, do not modify the methane formation. Other mechanisms should be used to explain the presumed formation of "early", non biogenic, methane, but, due to the mobility of methane in nature, arguments are only experimental or theoretical, but no direct evidence can be brought.