The effect of the nature of the cation on the surface and catalytic properties of calcium, strontium, barium and lead hydroxyapatites and dicationic analogs containing lead and strontium or barium has been studied with methanol and deuterated methanol. XRD, XPS and (3)1P MAS NMR have been used to characterize the samples, and temperature programmed desorption of deuterated methanol has been employed to provide ancillary information. The dehydration/dehydrogenation of methanol is found to depend strongly on the nature of the divalent cation and is related to the binding strengths of methanol on the hydroxyapatites.