Abstract Interpolyelectrolyte complexes (IPEC) have been used in different fields, ranging from biomedicine to oil exploration. Particle dimension is a key parameter for the use of an IPEC for a particular application. In this work, dynamic and static scattering (in the form of optical DLS and SAXS, respectively) were used to follow particle growth as a function of anionic/cationic polyelectrolyte mass ratio, w A C , coupled to turbidimetry, conductometry, viscometry, and zeta potential measurements. Turbidimetry, conductometry, and viscometry showed that at w A C ≅ 2 the IPEC dispersions presented changes that were associated to a massive production of IPEC particles. At the same w A C value, zeta potential measurements indicated an apparent isoelectric point, showing that this w A C must be related to a stoichiometric point for IPEC formation. Double KWW equation was adjusted to data from DLS intensity correlation functions, and parameters related to the distribution of relaxation rates presented characteristic changes at the same value of w A C . SAXS was used to follow particle growth until massive IPEC production. It showed that particles firstly were in the form of small, globular particles, tending to unfolded chain geometry, which can be related to the occurrence of flocculation, just at the point of massive IPEC production.