The generation and accumulation of an electrostatic charge from handling pharmaceutical powders is a well-known phenomenon, given the insulating nature of most APIs (Active Pharmaceutical Ingredients) and excipients. In capsule-based DPIs (Dry Powder Inhalers), the formulation is stored in a gelatine capsule placed in the inhaler just before inhalation. The action of capsule filling, as well as tumbling or vibration effects during the capsule life cycle, implies a consistent amount of particle–particle and particle–wall contacts. A significant contact-induced electrostatic charging can then take place, potentially affecting the inhaler’s efficiency. DEM (Discrete Element Method) simulations were performed on a carrier-based DPI formulation (salbutamol–lactose) to evaluate such effects. After performing a comparison with the experimental data on a carrier-only system under similar conditions, a detailed analysis was conducted on two carrier–API configurations with different API loadings per carrier particle. The charge acquired by the two solid phases was tracked in both the initial particle settling and the capsule shaking process. Alternating positive–negative charging was observed. Particle charging was then investigated in relation to the collision statistics, tracking the particle–particle and particle–wall events for the carrier and API. Finally, an analysis of the relative importance of electrostatic, cohesive/adhesive, and inertial forces allowed the importance of each term in determining the trajectory of the powder particles to be estimated.