A small molecule donor TiC12 with an asymmetric thieno[3,2-c]isochromene unit is incorporated into the PM6:Y6 system as the third component for constructing ternary organic solar cells (OSCs). It was found that TiC12 played an outstanding role in improvement of open-circuit voltage (V-oc), short-circuit current (J(sc)) and fill factor (FF) for the OSCs. The effects of TiC12 on the absorption, exciton dissociation, charge extraction, bimolecular recombination and morphology of the active layer are analyzed in detail. The synergetic improvement of J(sc), V-oc and FF parameters is realized to generate an advanced power conversion efficiency (PCE) of 17.25% in the optimized PM6 : TiC12 : Y6 (0.9 : 0.1 : 1.2) ternary device. Furthermore, the V-oc is increased in proportion to the added amount of TiC12 in the ternary devices due to reduced disorder and nonradiative energy loss, although the guest donor TiC12 exhibited a higher HOMO level than PM6. This study provides an effective and innovative approach to elevate V-oc and thus PCE for ternary OSCs by introducing a guest small molecule donor with a higher HOMO level and better miscibility with the acceptor.