The type specimen of peisleyite has been reinvestigated by a combination of scanning electron microscopy, electron probe microanalysis (EPMA) and synchrotron powder X-ray diffraction. Morphological investigation showed that mats of peisleyite crystals, individually <3 μm across, are intergrown with wavellite veinlets to form the white cryptocrystalline material that is typical of ‘peisleyite’. New EPMA data (mean of 12 analyses) gave the empirical formula of peisleyite as (Na1.69Ca0.18)Σ1.87(Al9.04Fe0.03)Σ9.07[(P6.28S1.38Si0.25)O4]Σ7.91(OH)6.66·27.73H2O, or ideally Na2Al9[(P,S)O4]8(OH)6·28H2O. The associated wavellite was found to be F-rich. Synchrotron powder data were indexed and refined and gave the following unit cell: P1̄, a = 9.280(19), b = 11.976(19), c = 13.250(18) Å, α = 91.3(1), β = 75.6(1), γ = 67.67(1)°, V = 1308(5) Å3 and Z = 4. These data are significantly different to those reported in the original description of peisleyite.