Clay mineral ‘Crystallinity Index Standards’ (CIS) composed of Palaeozoic mudrocks from southwest England were investigated systematically in five sub-fractions per sample for the first time. X-ray diffraction was used to determine mineral assemblages, calibrated 001 illite full-width-at-half-maximum (FWHM) values and illite polytype compositions, in addition to K–Ar isotopic analyses of all fine fractions. The FWHM results of the <2 µm fraction are consistent with previous studies and reflect the range of diagenetic to epizonal grades covered by the sample set SW1 to SW7 (~0.61–0.26°2θ). Diagenetic and lower anchizone samples also show significant broadening of 001 illite reflections in the finer fractions and contain mixtures of authigenic 1M + 1Md illite and detrital 2M1 white mica polytypes suitable for illite age analysis. The estimated end-member ages of the Bude (SW1-1992) and younger Crackington (SW3-2000) mudstones yield detrital ages of Late Cambrian to Middle Ordovician (493–457 Ma) and a broad range of 1M + 1Md illite ages between Middle Permian and Early Jurassic (271–190 Ma). The detrital age of the stratigraphically older Crackington Formation mudrock (SW2-1992) is Late Devonian (384–364 Ma) with 1M + 1Md illite ages between Late Triassic and Early Jurassic (219–176 Ma). The origin of Mesozoic 1M + 1Md illite ages may represent neocrystallized illite associated with Mesozoic hydrothermal events or similar events that thermally reset older authigenic illite with partial loss of radiogenic argon and no renewed crystal growth. In contrast, upper anchizonal and epizonal Devonian slates (SW3-2012, SW4-1992, SW6-1992 and SW7-2012) contain only the 2M1 polytype, with K–Ar ages younger than the stratigraphic age. The three finest fractions of SW4-1992 yield consistent Late Carboniferous ages (331–304 ± 7 Ma) that are considered to date the neocrystallized 2M1 mica. Most fractions of epizonal slate (SW6-1992, SW7-2012) yield Early Permian ages (293.6–273 Ma) corresponding to published cooling ages of the Tintagel High-Strain Zone and the intrusion of the Bodmin granite (291.4 ± 0.8 Ma). These first K–Ar age constraints for the fine fractions of the CIS should provide useful reference values for testing analytical procedures of illite age analysis.