The results of traditional methods of coal characterisation (proximate, specific energy, and ultimate analyses)for 28 Eocene coal samples from the West Coast of New Zealand correspond well with biomarker ratios and Rock-Eval analyses. Isorank variations in vitrinite fluorescence and reflectance recorded for these samples are closely related to their volatile-matter content, and therefore indicate that the original vitrinite chemistry is a key controlling factor. By contrast, the mineral-matter content and the proportion of coal macerals present appear to have had only a minor influence on the coal samples＇ properties. Our analyses indicate that a number of triterpane biomarker ratios show peak maturities by high volatile bituminous A rank; apparent maturities are then reversed and decline at the higher medium volatile bituminous rank. The Rock-Eval S1 + S2 yield also maximizes by high volatile bituminous A rank, and then declines; however this decline is retarded in samples with the most hydrogen-rich (perhydrous) vitrinites. These Rock-Eval and biomarker trends, as well as trends in traditional coal analyses, are used to define the rank at which expulsion of gas and oil occurs from the majority of the coals. This expulsion commences at high volatile A bituminous rank, and persists up to the threshold of medium volatile bituminous rank (c. 1.1% Ro ran. or 1.2% Ro max in this sample set), where marked hydrocarbon expulsion from perhydrous vitrinites begins to take place.