Contact electrification (CE), where opposing surfaces become strongly charged after contact with one another, is an intriguing and powerful phenomenon, attributed broadly to friction and subsequent charge transfer between two dissimilar materials. In the case of contact between metal−metal,[1] metal−ceramic,[2] and ceramic−ceramic[3] interfaces, CE is well understood to arise from electron transfer. However, the source of charge remains ambiguous for organic interfaces (e.g., polymers) undergoing CE. Commonly, in the energy harvesting community, CE between two polymers is rationalized through an electron-transfer mechanism between the materials, leading to the establishment of the triboelectric series[4]. Due to the lack of free electrons in dielectric or ferroelectric polymer materials, it is unlikely that electron transfer alone can explain the large charges and voltages measured from CE. Herein, the effect of cohesive energy on measured CE in polymers is discussed. Rigorous experiments involving contact between a polymer and another polymer; glass; and liquid metal demonstrate an equivocal trend where cohesive energy is broadly inversely proportional to the measured CE. This study provides a new way to consider triboelectrification from polymers and provides guidelines to predict the magnitude and sign of the generated surface charge from CE.