Brinrobertsite, an ordered, mixed-layered, dioctahedral pyrophyllite-smectite (P/S), occurs in a metabentonite in the Ordovician Nant Ffrancon Formation near Bangor, N Wales. It comprises ~30% of the metabentonite, in association with quartz (~50%) and chlorite (clinochlore; 20%) which replaced glass shards and fine-grained glass matrix. Transmission electron microscopy (TEM) images show sequences of dominant ~24 Å 001 lattice fringes inferred to correspond to 2:1 layers with alternate pyrophyllite-like (low-charge) and smectite-like (higher-charge) interlayers (i.e. R1 ordering). The hk0 diffraction patterns are mostly hexanets with some spotty circles, implying that layers are largely coherently related, but with some turbostratic stacking. Collective data show that d100 = 5.2, b = 9.1, and d001 = 24–25 Å, assuming monoclinic or pseudomonoclinic symmetry. The composition, as determined by energy dispersive spectral analysis, is (Na0.22K0.07Ca0.06)(Al3.81Mg0.08Fe0.08)(Si7.84 Al0.16)O20(OH)4·3.54H2O, as consistent with the sum of the compositions of pyrophyllite-like and smectite-like units. Water content was determined by DTA/TGA analysis. The powder diffraction patterns have a principal peak with d001 = 24.4 Å. Patterns of air-dried and glycol-saturated brinrobertsite, including Na- and Ca-saturated and untreated samples, were modelled satisfactorily as R1-ordered P/S by the program NEWMOD-for-Windows™. The unique composition of brinrobertsite relative to R1 IS, which is ubiquitous in metabentonites, was caused by leaching of alkalis and alkaline-earth elements by hydrothermal fluids associated perhaps with a nearby intrusion, as demonstrated by bulk-chemical analyses of the metabentonite. The crystal structure is modelled as having Al/Si distributions symmetrical by reflection across interlayers. This causes all 2:1 layers to be equivalent in having one tetrahedral sheet with little or no Al, and the other with significant Al substitution, giving rise to alternate high- and low-charge interlayers. Geological evidence suggests that brinrobertsite is a back-reacted product of hydrothermal alteration in the sequence: glass → pyrophyllite → brinrobertsite.