The relationship between chemical structure and reactivity for thermal hydroprocessing was studied for five gas oils derived from Alberta bitumens. Chemical structure was characterized by combining data from 1 H and 13 C nuclear magnetic resonance spectroscopy, class fractionation, and elemental analysis to calculate structural parameters. Thermal hydrotreating was performed in a continuous‐flow stirred reactor at 420 and 440°C, 13.9 MPa hydrogen pressure, and 1.5 h1 LHSV. Conversion of the 343–525°C boiling fraction of the gas oils was correlated with the concentration of naphthenic methylene groups in the feed. Formation of methane and ethane was dependent on the degree of condensation of the aromatic rings in the feed oils. Thermal desulfurization was highly correlated with the amount of saturates in the feed, and the aromaticity of the resin fraction. Hydrogen consumption increased with the aromaticity of the gas oil…