Fabrication of an anode with high specific capacity is one of important strategies for improve the energy density of Li-ion batteries (LIBs). In present work, a ceramic target of Li-doped NiO solid solution (Ni0.96Li0.04O, denoted as NLO) was prepared for fabricating nanostructured thin films using magnetron sputtering. The electrochemical performance of prepared thin films for electrode application in LIBs was investigated. Compared with the undoped thin film, the predoped NLO thin films exhibited superior overall performance. The predoped NLO thin films provided an initial discharge specific capacity of 785 mAh g−1 (173 μAh cm−2) at 0.2C and maintained 666 mAh g−1 after 100 cycles, while the undoped NiO thin flm showed the ones of 534 and 319 mAh g−1, respectively. The predoped NLO thin films demonstrated outstanding rate performance with specific capacities ranging from 798 mAh g−1 at 0.2C to 384 mAh g−1 at 3.2C. Influence of pre-solid-solution doping on the superior electrochemical performance of NLO film was discussed taking account on predoping enhanced electronic conductivity of the thin films.