A simple yet versatile solution-based process to produce colloidal silica hexapods is developed in which various shapes of silica rods are grown on the faces of cubes in a controlled manner. In the presence of hematite cubic particles, water droplets nucleate on the surface of hematite by phase separation in pentanol. By adjusting the water concentration, six droplets can form on each face of the hematite cube. A silica precursor is then administered into the system, which gradually diffuses into the water droplets through the oil phase. Within the droplets, hydrolysis and condensation of the precursors take place, leading to formation of silica rods. As a result, silica hexapods on a magnetic hematite cubic seed are produced. Furthermore, when the emulsions are aged at 60 °C prior to the silica growth, the water content in the solution decreases gradually due to evaporation and spiky sharp hexapods are produced. On the other hand, when organosilane precursor is added, pancake-like hexapods are formed due to the reduction of interfacial tension. These colloidal hexapods can further be utilized as new building blocks for self-assembly to construct functional materials or as a model system to understand collective behaviors.