The initial-stage dynamics of flocculation of positively charged latex particles induced by polyelectrolytes (PEs) and polyelectrolyte complexes (PECs), composed of linear polyacrylic acid (PAA) and a PAA-based hydrophilic microgel (PAA#) with a small amount of a linear polycation, was comparatively analyzed by applying the standardized colloidal mixing procedure. Based on the rate of flocculation, this method allows us to investigate the dynamics of flocculation immediately after the onset. In addition to confirming the prediction made regarding the initial rate of flocculation with linear polyanions—which was mostly similar to that observed in negatively charged colloids with positively charged PEs—we have confirmed two important new results regarding the microgel: (1) the increase of the initial rate is less markedly affected by the microgel concentration than by the linear polymer concentration, which can be explained by the fact that the three-dimensional (3D) cross-linked structure of the microgel that does not deform as easily as the linear structure upon touching the colloidal surface; and (2) there is a remarkable increase of the initial rate due to the contribution of instant aggregation of the negatively charged microgel induced by the polycation adsorption. These results suggest the significance of state and formation dynamics of PECs prior to reaching the surface of targeted colloidal particles for the intension of effective flocculation. These aspects are not treated so far in the dynamic process of flocculation.