Fe3O4 nanoparticles with cluster structure are superparamagnetic particles with applicability in various high-tech fields. In this study, the influence of surface modification with polyacrylic acid (PAA), a polymeric precursor, on the characteristics of Fe3O4 nanoparticles was investigated. The particles were synthesized by the polyol method and surface modified with various amounts of PAA. The surficial, structural, optical, and magnetic properties of the PAA-modified Fe3O4 nanoparticles were analyzed, confirming that negatively charged carboxyl groups were formed on the particle surface, and the particle dispersibility was enhanced by surface modification. This arises from an increase in the electrostatic repulsive force due to the surface functional groups. Functionalization promoted dissociation of the cluster particles, which became more pronounced as the PAA content increased. The optical parameters changed with the PAA content. Analysis of the magnetic properties showed that the saturation magnetization decreased as the PAA content increased. Overall, PAA modification induces structural changes of the Fe3O4 nanoparticles that enhance the dispersibility and influence the characteristics of the particles.