Clustering of fine particles is of crucial importance in settings ranging from the early stages of planet formation [1][2][3] to the coagulation of industrial powders and airborne pollutants [4][5][6][7] . Models of such clustering typically focus on inelastic deformation and cohesion 1,4,6,8 . However, even in charge-neutral particle systems comprising grains of the same dielectric material, tribocharging can generate large amounts of net positive or negative charge on individual particles, resulting in long-range electrostatic forces [9][10][11] . The e ects of such forces on cluster formation are not well understood and have so far not been studied in situ. Here we report the first observations of individual collide-and-capture events between charged submillimetre particles, including Kepler-like orbits. Charged particles can become trapped in their mutual electrostatic energy well and aggregate via multiple bounces. This enables the initiation of clustering at relative velocities much larger than the upper limit for sticking after a head-on collision, a long-standing issue known from pre-planetary dust aggregation 1,12 . Moreover, Coulomb interactions together with dielectric polarization are found to stabilize characteristic molecule-like configurations, providing new insights for the modelling of clustering dynamics in a wide range of microscopic dielectric systems, such as charged polarizable ions, biomolecules and colloids [13][14][15][16] . One of the key difficulties in studying the interplay between repulsive contact forces, short-range cohesion and long-range electrostatic forces during cluster formation has been to obtain sufficiently detailed experimental data. Seeing how this process unfolds demands in situ observation of the collision trajectories among charged grains to extract quantitative information about their interactions. This requires the grains to be freed from gravity and tracked with high spatial and temporal resolution to capture individual collision events 17,18 . We overcome these obstacles with the set-up shown in Fig. 1a (refs 19,20). The granular material, in our experiments fused zirconium dioxide-silicate grains a few hundred micrometres in diameter, is contained in a vessel mounted inside a 3.0-m-tall cylindrical chamber. We evacuate this chamber to mitigate air drag. When a shutter covering a small orifice at the bottom of the vessel is opened, particles fall out freely, forming a dilute stream. Outside the chamber, a high-speed video camera falls alongside the grains, guided by low-friction rails. In the co-moving frame seen by the camera, the effect of gravity is eliminated, making it possible to track particle interactions in detail for about 0.2 s until the camera is decelerated by a foam pad. The same apparatus also allows determination of the net charge on individual grains: during free fall a horizontal electric field can be applied and the resulting horizontal acceleration observed by the camera gives the charge to mass ratio, q/m.Using particles with a narrow size d...