The understanding of triboelectric charging of industrially important powders can help in avoiding or controlling the particle agglomeration and wall sheeting. We developed a new experimental approach to study both samematerial particle-particle (P\ \P) and different-material particle-wall (P\ \W) charging of nascent polyethylene (PE) particles born by catalytic polymerization. We constructed a simple tribocharger consisting of a metal box divided inside into several compartments filled with the PE sample and attached to the vibration shaker. The particle charge distribution was characterized by a self-constructed electrostatic separator. This way, we investigated the charging dynamics of PE particles colliding with other PE particles as well as with metal walls of the box compartments. Both P\ \P and P\ \W charging were measured either separately, or in sequence, and in combination of simultaneous P\ \P and P\ \W. The different-material P\ \W charging produced unipolarly charged particles and was much faster than the same-material P\ \P charging leading to bipolar particle charge distribution.