The nucleation and growth of polystyrene (PS) nodules on 170 nm silica seeds under emulsion-polymerization conditions have been investigated for the first time by cryo-electron tomography. 3D arrangements were reconstructed from samples collected at several polymerization times (from 5 to 120 min). Early samples display the presence of small PS nodules bound to silica particles in a random distribution. For longer polymerization times, the number of PS nodules per silica seed decreases leading to octopod-like morphologies. The tomographic method allowed us to measure the contact angle that the growing PS nodules form with the silica bead surface. The average value of 142.4° remains constant over all of the observed period of the polymerization reaction. This contact angle appeared to be one of the key parameters for controlling the morphology of PS–silica biphasic particles.