We report first on the interpolyelectrolyte complex formation (PEC) between one polycation of integral type having about 95 mol% of N,N-dimethyl-2-hydroxypropyleneammonium chloride units in the backbone (PCA(5)) and poly(sodium styrenesulfonate) (NaPSS), in dependence on the polyion concentrations and the mixing order. The PEC formation was qualitatively followed by viscometry, conductometry and UV-spectroscopy. Quasi-soluble PECs could be formed in the polyion concentration range of 0.1-1.0 unit mM. A complex stoichiometry close to 1:1 was found by both the qualitative measurements on the formation of quasi-soluble PEC in dilute aqueous solutions (when PCA(5) concentration was lower than the overlap concentration, C < C*) and elemental analyses of the insoluble PEC formed at the high polycation concentration (50 unit mM, C much greater than C*). The influence of the ionic strength on the PECs stability was followed by the subsequent addition of NaCl up to an ionic strength of 3.5 M on the reaction mixture, after the PECs formation with three polycations different by both the content of quaternary ammonium salt groups in the backbone and the degree of branching (PCA(5), PCA(20) and PCT20). No dissociation of PECs into the original components was evidenced irrespective of the polycation structure and the mixing order.