The proton and carbon-13 nuclear magnetic resonance characteristics of the native Whiterocks bitumen were determined by comparing the spectra of the samples to literature assignments. The tentative structural assignments of pyrolysis products were also obtained from the spectra of Curie-point low voltage mass spectrometric analysis. The results obtained from proton and carbon-13 nuclear magnetic resonance and pyrolysis-mass spectrometry analysis suggested that the native bitumen consists mostly of short- and long-chain (i.e., normal and isoprenoid chains) alkylsubstituents attached to polycyclic naphthenic, naphtheno-aromatic and/or aromatic moieties.