Lithium-rich layered oxides (LRLO) have raised the greatest attention to the high-energy-density Li-ion batteries. Nevertheless, the undesirable interfacial side reactions and the structure transformation causes fast voltage fading and poor capacity retention of LRLO cathodes, which extremely prevent their practical application. Surface coating or lattice doping has been an effective strategy to improve its electrochemical properties. However, the general performance of the material can only be limitedly promoted. Herein, we proposed a bifunctional modulation of LRLO cathodes coupled by bulk-phase W-doping and surficial Li2WO4 nano-coating of LRLO using a facile synchronous lithiation strategy under a high-temperature solid-state treatment. The modified material (2 mol% W6+ modified) showed a distinguished discharge capability of 260.5 mA h g−1 at 0.1 C after 50 cycles. Meanwhile, a competitive capacity retention of 95.38% at 1 C after 100 cycles were achieved. The splendid electrochemical performance can be the result of the increased inter-layer spacing for enhancing Li+ diffusion kinetics and the stronger W-O bond for alleviating oxygen release after W-doping, and Li2WO4 nano-coating which not only accelerates the Li+ transfer rate as its fast Li+ transfer channels but also act as a transitional interface layer to restrain the interfacial adverse reactions.