Corrensite and chlorite-rich chlorite-smectite (Chl-S) mixed-layers occurring in the Macigno Formation of northwestern Tuscany were investigated by XRPD/SEM techniques. The samples from the Macigno outcrops were affected by metamorphism corresponding to the high-diagenesis/low-anchizone transition boundary. The basal spacing of corrensite measured from 00l reflections on EG–Mg2+-saturated samples ranges from 30.97 to 31.18 Å with a coefficient of variation (CV) of 0.46–0.77%, consistent with the rational pattern of a 1:1 Chl-S periodic stacking sequence. X-ray patterns of heated K+-saturated specimens reveal the presence of two types of corrensite, probably with different interlayer charges on their respective smectite-like layers. The chlorite-rich Chl-S mixed layers coexisting with corrensite consist of R2 chlorite (0.70–0.75)/S and chlorite (0.90)/S with long-range ordering R ⩾ 1. SEM observations show that corrensite and chlorite-rich Chl-S mixed-layers are closely mixed on a sub-micron scale. Some grains of corrensite and chlorite-rich Chl-S mixed-layers include zones (2–10 μm) of chlorite composition, as shown by microprobe analyses.