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The Buller Coalfield in the northern portion of the Paparoa Trough (NW South Island, New Zealand) contains a middle Eocene bituminous coal‐bearing succession that exhibits marked variations in both coal rank and type. The across‐basin rank changes result from differential late Palaeogene subsidence of the Paparoa Trough and subsequent inversion. Superimposed upon coalification trends are down‐seam variations in coal type, evidenced by isorank variation in conventional chemical parameters. These type variations are not a consequence of changes in maceral group proportions, which are dominated by vitrinite. Forty‐eight coal samples from fifteen drillholes through the Brunner Coal Measures have been examined for vitrinite reflectance, proximate analysis, specific energy, and sulphur content. Total Organic Carbon (TOC), Rock‐Eval properties and the bulk composition of the bitumen were also determined. All the coals analysed lie within the high volatile bituminous B to medium volatile bituminous coalification stages. Variation in analytical properties within this suite, and more specifically within serial samples, provides insights into the nature of the organic matter comprising the coals. While TOC varies systematically with ash content, reflecting proximity of the depositional mires to fluvial systems, values increase with rank (68–86% ash free). The Hydrogen Index (HI) decreases from 334 to 190 mg hydrocarbons/g TOC over a range of 429 to 470 d̀C Tmax, analogous to the volatile matter content and vitrinite reflectance, respectively. The more perhydrous coal samples at a given rank are characterised by depressed Tmax/vitrinite reflectance and elevated Hi/volatile matter contents. Bitumen and sulphur contents are not the primary control onperhydrous characteristics. The bitumen content crudely corresponds to the S1 peak plus the initial portion of the S2 peak liberated under low temperatures during Rock‐Eval pyrolysis; however, the bulk of the generative potential is associated with the residual kerogen fraction. Suggate (S) Rank and maximum palaeotemperature appear to be the best indicators of coal rank. A period of significant hydrocarbon generation and release begins at Tmax∼440d̀C for the Buller coals. The main oil “window” is defined by the interval 440–455d̀C Tmax or 0.8–1.1% vitrinite reflectance (Romax), and by correlation to maximum palaeo‐temperatures, 125–155d̀C. This is further substantiated by mass balance considerations, which indicate that hydrocarbon generation (Petroleum Generation Index (PG1) > 0.1) was occurring in the coals at a maturity level of O. 7–0.9 % Romax (Tmax 440–444 d̀C) with an increase in PGI between ∼0.9 and 1.1% Romax (∼Tmax 445–455 d̀C). Between PGI 0.1 and 0.4, the expulsion efficiency rapidly increased, presumably due to generation and expulsion of the bulk of the oil.