The morphologies of several ionotropic alginate hydrogels and aerogels were investigated by SAXS according to the nature of the divalent metal cation (Mn2+, Co2+, Zn2+, Cu2+) and the guluronic fraction of the alginate. All alginate hydrogel and aerogel samples show isotropic small-angle X-ray scattering. Gelation results from cooperative associations of cations and chain segments and yields different nanostructures, that is, nanofibrillar morphology or multiple junction morphology, according to cation type and eventually mannuronic/guluronic ratio. Therefore, Mn and Cu gels present the same morphology whatever the guluronic ratio, whereas Co and Zn gels yield different nanostructures. In the size range investigated by SAXS (similar to 10-200 angstrom), the structure of aerogels obtained by CO2 supercritical drying is found to be inherited from the morphology of the parent hydrogel whatever the initial structural regime.