By using optical electric-field-induced second-harmonic generation (EFISHG) technique, we studied carrier behavior caused by contact electrification (CE) in an organic double-layer element. This double-layer sample was half suspended in the open air, where one electrode (anode or cathode) was connected with a Cu foil for electrification while the other electrode was floated. Results showed two distinct carrier behaviors, depending on the (anode or cathode) connections to the Cu foil, and these carrier behaviors were analyzed based on the Maxwell-Wagner model. The double-layer sample works as a simple solar cell device. The photovoltaic effect and CE process have been proved to be two paralleled effects without strong interaction with each other, while photoconductivity changing in the sample can enhance the relaxation of CE induced charges. By probing the carrier behavior in this half-suspended device, the EFISHG technique has been demonstrated to be an effective non-contact method for clarifying the CE effect on related energy harvesting devices and electronics devices. Meanwhile, the related physical analysis in this letter is also useful for elucidating the fundamental characteristic of hybrid energy system based on solar cell and triboelectric nanogenerator. (C) 2016 Elsevier B.V. All rights reserved.