Powders may become electrostatically charged due to friction. This phenomenon may lead to unusual outcomes such as increased cohesion, adhesion, and poor flow. It is still a challenge to investigate the electrostatic properties of powders due to restrictions associated with existing methods. The objective is to present a novel coupling method with the dynamic vapor sorption (DVS) instrument using a capacitive probe to measure the electrostatic potential of powders. The critical factors affecting measurements are defined to aid experimental design. The method was tested with glass beads tribocharged after contact with stainless steel to assess the feasibility of the setup via analysis of the repeatability and reproducibility of the data generated. The results obtained show that electrostatic measurements can be performed with minimum noise interference, short equilibration time of 15 min, and high reproducibility based on 19 measurements. Stability of experimental conditions of ±0.1 °C and ±0.2% RH is achieved.