The aim of the work was to find the relationship between the structure of the stationary phase and the velocity of the electroosmotic flow (EOF) that it can generate. The attention was paid to the dependence of the electroosmotic mobility (microEOF) on such parameters as: (i) coverage density of a series of specially synthesized C18 stationary phases with/without end-capping, with monomeric/polymeric architecture; (ii) the length of the alkyl chain in the alkylamide (AP) bonded phase (the phases studied were AP with: C1, C5, C6, C7, C8, C12 and C18 alkyl chains) and the effect of the presence of amide and residual amine groups; (iii) the effect of the mobile phase composition on the EOF; (iv) the effect of pH on the EOF. The obtained results have shown that there is no direct relationship between silanol activity (Galushko test) and electroosmotic mobility for C18 phases. The deterioration of the EOF has been observed for AP phases at high pH values. This effect has been attributed to the presence of hydrolytic pillow, which is connected with the sorption of water from hydro-organic mobile phases.