In this work, three carboxymethyl starches (CMS) were obtained by the two-step reaction process of carboxymethylation with different degrees of substitution (0.16, 0.33, and 0.36). From these samples, (bio)polyelectrolyte complexes ((bio)PECs) were obtained with chitosan (Chit) by the mixing of individual solutions of polymers (0.25 wt.%) at different volume ratios. The effect of the biopolymer and ionized groups of z ratios, pH, and degree of substitution of CMS in the formation of PEC were evaluated by turbidimetry and dynamic light scattering. The results showed that increasing the amount of CMS samples (ratio of z) led to an increase in the efficiency of the formation of (bio)PEC using CMS with a high DS value. Using the turbidimetry method for the chitosan and CMS mixtures, it was observed that the formation of (bio)PEC is divided into four transition zones delimited by pH transition points, and the stoichiometric complexation (z = 1) is achieved at a pH that displayed morphological changes “pH_morph”, which is a single point for Chit:CMS 1, and for Chit:CMS 2 and Chit:CMS 3, this is a range of 4.9–6.4 and 4.3–6.4, respectively. Analysis of the structural properties of the structures of (bio)PECs by dynamic light scattering was characterized by monomodal distribution, and the main observed effect was associated with an increase in the value of D_avg with an increase in the ratio of Chit:CMS.