Acrylonitrile-grafted poly(vinyl alcohol) copolymer with a branched structure is synthesized and used as binder for a LiNi1/2Mn3/2O4 composite electrode. Electrode performances of composite electrodes with different binders are compared in Li cells at 50 °C. The branched copolymer has better coatability to active materials in comparison to a simple mixture of linear polymers and conventional PVdF as evidenced by hard X-ray photoelectron spectroscopy. Cyclability is effectively improved by using the branched copolymer at elevated temperatures because of high chemical stability of the coated polymer layer and formation of a protective layer on cycles. Moreover, excellent rate-capability is realized by applying the branched copolymer with high adhesive strength, and the composite electrode delivers 70 mAh g−1 of discharge capacity at a rate of 1280 mA g−1.