We present structural and turbidimetric characterizations of aqueous dispersions of oppositely charged nanoparticles and polyelectrolytes that undergo complexation and flocculation to form particle-rich agglomerates over a wide range of polyelectrolyte and nanoparticle concentrations with varying polyelectrolyte sizes and persistence lengths. Compaction of nanoparticles in the polyelectrolyte-nanoparticle complexes, signified by decreasing internanoparticle spacing until they are brought in near-contact, is observed upon increasing screening of interparticle repulsion arising from adsorption of polyelectrolytes on the nanoparticle surfaces. We identify the ratio of charge borne by the polyelectrolytes and the nanoparticles as a key parameter dictating the compaction of nanoparticles into complexes as well as densification of complexes into agglomerates. Moreover, the emergence of turbidity in solution is shown to correlate with the initiation of nanoparticle compaction by polyelectrolytes but failing to describe further structural evolution of the complexes, emphasizing the need for alternate characterization techniques.