The charge transferability of the electron transfer layers (ETLs) is important for achieving high performance in mesoscopic (mp) perovskite solar cells (PSCs). However, because of the low electron extraction efficiency of TiO2, lithium doping is essentially required. In this work, we compared the electrical properties of mp-TiO2 doped with Li-salts with different anions-LiTFSI, Li2CO3, LiCl, and LiF. Interestingly, we found that the anions of the Li-salt dopants affect the electrical properties of the ETLs and the solar cell performance. The Li2CO3 doping of mp-TiO2 led to conduction bands deeper than those of pristine mp-TiO2 or other doped mp-TiO2. The maximum efficiency of 25.28% and certified efficiency of 24.68% (Newport) was obtained by using Li2CO3 dopant. This optimization of the ETLs properties is expected to greatly contribute to the progress of PSCs by leading to further increases in their efficiency.