Layered cathode materials LiNi0.5Co0.5O2 were successfully synthesized by microwave-assisted method using polyacrylamide (PAM) as template. Effects of the PAM concentration, sintering temperature and time on the morphology, microstructure and electrochemical performance of the materials were systematically investigated. X-ray diffraction (XRD) patterns reveal that the sample prepared with 8wt.% PAM and sintered at 1023K for 4h shows the best ordering layered structure with the maximum I(003)/I(104) ratio and the largest distance of splitting diffraction peaks of the crystal plants (006) and (012), (018) and (110). It can be seen that the above sample is composed of sphere-like particle from the scanning electronic microscopies (SEM) observation. The charge–discharge experiments indicate that the sample, compared with the samples prepared under other conditions, also has the best electrochemical properties, with the largest discharge capacity of 154mAh/g and the capacity retention of 145mAh/g after 20 cycles at a 0.2C rate between 3.0 and 4.3V. The study confirmed that the application of microwave is in favor of the formation of nuclei, which plays a key role in shortening the synthetic time and reducing the sintering temperature.