Heteroaggregation of colloids is an important yet complex physical process involving colloidal/nanosized particles and is relevant in river delta formation, paper-making, water treatment, blood flocculation, and so on. Despite the earlier studies on oppositely charged spherical colloids, heteroaggregation of colloids of different shapes is less explored. In this regard, we report an experimental study to investigate the colloidal stability of mixture of positively charged spheroidal hematite and negatively charged spherical silica nanoparticles. In this study, pH and surface area ratio (silica to hematite, SS-H) are varied to tune the colloidal stability/instability of the suspension. At pH 6.5 and low SS-H, the silica particles adsorb onto the hematite particles and reduce the effective charge of the latter, leading to aggregation and resulting in unstable dispersions. At higher SS-H, adsorption of silica on hematite leads to overcharging and charge reversal, which leads to a stable dispersion. Similar experiments were performed at pH 2.4 and 3.5, and the crossover from unstable to stable dispersion is observed as a function of SS-H. Calculation of Derjaguin, Landau, Verwey, and Overbeek (DLVO) interaction between particles in the binary mixture, as a function of pH and SS-H, based on the aggregate size and zeta potential, explains the transition from unstable to stable dispersion. The size and zeta potential of heteroaggregates in the dispersion were analyzed by dynamic light scattering (DLS) technique. Adsorption of silica nanoparticles on hematite particles was visualized by scanning electron microscopy (SEM). The study provides a framework based on DLVO interactions to stabilize or destabilize a colloidal dispersion of nonspherical particles by controlled addition of oppositely charged spherical colloids, which is a feat that is not possible with simple salt. The stability ratio (W) calculated from DLVO interactions demark the unstable-stable dispersion regions, which is found to be in agreement with the experimental results. © 2018 American Chemical Society.