Motivated by the requirements of performance stability in environments of variable humidity, the focus of this study is on the effects and role of humidity-induced water molecules and ions in the contact electrification (CE) mechanisms of triboelectric materials. In particular, the compatibility of direct charge transfer-based CE and other generally known or proposed water molecules or OH/H3O ion-facilitated CE mechanisms was assessed for a set of high-performance polymeric materials and functionalization molecules. The first set of test mechanisms included OH/H3O ion adsorption at the low-humidity limit. The adsorption resulted in physisorption or H transfer involving reactions that were not fully compatible with charge affinity-driven CE reactions on the considered contact surfaces for both ions in terms of the potential increase of the resultant density of surface charge. An alternative mechanism, which yielded compatibility at a large humidity limit, consisted of free energy-driven segregation and separation of the ions. Further test mechanisms included water adsorption-induced charge transfer and two mechanisms pertinent to charged material transfer: adsorption modulation due to formation of water monolayers and water solvation-induced separation of polymer fragments. According to the obtained results, both mechanisms could be verified as viable contributors to enhanced charge transfer. Consequently, the results allowed for conclusions regarding the general applicability of different, water-assisted CE mechanisms and the selection of particular pairs of contact materials of similar type for optimum performance in humid environments.