The triboelectrostatic separation allows the sorting of granular polymers according to their contact charging characteristics. It consists in the appropriate triboelectric charging of particles, followed by their selective sorting in an electrostatic field. Exposed to a humid atmosphere, the polymer granules adsorb water moisture onto their surfaces, which modifies their charging characteristics, by improving the contact between surfaces. The present work was aimed at studying the effect of storage environmental conditions on the triboelectric charging of granular polymers in vibratory-type devices. Four granular different plastic wastes were placed in a climatic chamber and kept for 96 hours under controlled humidity, RH = 82% ± 4%, at 19 °C ± 1 °C. The measurement of the water content of the polymer granules pointed out an increase of at least 10% after 96 h of exposure to high relative humidity ambient conditions. The granules were successively charged by triboelectric effect in a vibratory device equipped with recipients in two different materials, at ambient conditions. The tribocharging efficiency was analyzed by measuring the electric charge of the granules with a Faraday pail connected to an electrometer. The thin water layer formed at the surface of the particle can explain their modified triboelectric behavior. The difference between the triboelectric charging behavior of “humid” and “normal” polymer granules depended also on the nature of the recipient of the tribocharging device.