We investigate the link between the microstructure, dynamics, and rheological properties in dense (phi = 0.3) mixtures of charge-stabilized colloidal silica and oppositely charged poly(ethylene imine) polymer in a mixed DMSO/H(2)O solvent. Over a finite range of polymer concentrations, the addition of polymer results in the formation of sample-spanning, self-supporting gel networks. As the polymer concentration is increased, a reentrant rheological transition is observed where the gel's elastic modulus and yield stress initially increase and subsequently drop. The dynamic and microstructural changes associated with this transition are resolved using quantitative confocal microscopy. Within the initial regime, a biphasic system consisting of a mixture of arrested and diffusive particles is observed. We segregate the particles with high accuracy into mobile and arrested populations based on their dynamics. The addition of polymer in this regime systematically decreases the proportion of free particles, until all the particles are arrested. Concurrent with this transition, the elastic modulus and yield stress go through their corresponding maxima. However, over the range of polymer concentrations studied, the reentrant transition to weak gels is not captured by the particle dynamics but is instead accompanied by subtle changes in the microstructure of the arrested phase. We discuss two possible scenarios for this behavior in view of the strength of interparticle bonds.