A set of chromatographic materials for bioseparation were characterised by various methods. Both commercial materials and new supports presenting various levels of rigidity were analysed. The methods included size-exclusion and capillary phenomena based techniques. Both batch exclusion and inverse size-exclusion chromatography were used. Gas adsorption, mercury porosimetry and thermoporometry were applied as well as a new method based on water desorption starting from the saturated state. When the rigidity of adsorbents is high enough, the agreement is reasonable between the values of the structural parameters that were determined (surface area, porosity, and pore size) by various methods. Nevertheless, a part of macroporosity may not be evidenced by inverse size-exclusion chromatography whereas it is visible by batch exclusion and the other methods. When the rigidity decreases, for example with soft swelling gels, where standard nitrogen adsorption or mercury porosimetry are no more reliable, two main situations are encountered: either the methods based on capillary phenomena (thermoporometry or water desorption) overestimate the pore size with an amplitude that depends on the method, or in some cases it is possible to distinguish water involved in the swelling of pore walls from that involved in pore filling by capillary condensation.