Gold-tube pyrolysis experiments were performed on two Athabasca oil sand bitumens at 300 °C to 525 °C with 2 °C/h rate and 25 °C step under 50 MPa. Pyrolysis temperature of 425 °C is critical for weight loss of bulk bitumen and hydrocarbon generation and destruction. Polar compounds are the main source of saturated and aromatic hydrocarbon, gas and coke fractions. Molecular compositions in pyrolyzates vary systematically with increasing pyrolysis temperatures. High molecular weight n-alkanes (C26+) are gradually destructed during pyrolysis due to thermal cracking. Moderate molecular weight n-alkanes (C21–C25) show the highest thermal stability in designed pyrolysis temperatures. The loss of low molecular weight n-alkanes (C20−) might be caused by volatilization during pyrolysis, which may alter commonly used molecular parameters such as ∑n-C20−/∑n-C21+, Pr/n-C17 and Ph/n-C18. Aromatic hydrocarbons were generated from 300 to 425 °C, then condensation and dealkylation have been initiated at 425 °C as evidenced by decreased summed alkylnaphthalenes to alkylphenanthrenes ratios and increased unsubstituted aromatics to substituted homologs ratios in higher temperatures. The occurrence of anthracene and benz[a]anthracene in pyrolysates indicates pyrogenic origin, while fluoranthene shows unexpected behaviors during pyrolysis. Ratios derived from them are not always reliable for pyrogenic source input diagnosis in environmental samples.