Conventional additives like 1,8-diiodooctane (DIO) and 1-chloronaphthalene (CN) play an essential role in optimization of blend film morphology of polymer solar cells (PSCs). However, they have halogenated elements in their end groups, which are harmful to the environment and humans, limiting large-scale applications. In this work, a novel non-toxic and non-halogen additive, dibenzyl ether (DE), was introduced into PTB7-Th:PC71BM based PSCs, and the role of the DE additive was systemically investigated. The results showed that DE additive can not only adjust phase separation and optimize the morphology of blend film, but also promote the mobility of hole and electron. The grazing-incidence small-angle X-ray scattering (GISAXS) showed that the introduction of DE increased the interface area between PTB7-Th and PC71BM, which can promote exciton dissociation, and achieve better charge transport. Transient photovoltage (TPV) and transient photocurrent (TPC) measurements show that carrier recombination of the additive-containing devices can be effectively inhibited with improved charge transport efficiency of the active layer. Consequently, the devices with DE additive achieve power conversion efficiency (PCE) of 9.53% and a fill factor (FF) of 70.41%. Our non-toxic and non-halogen additive provides a potential solution for the preparation of environmental-friendly PSCs in the future.