AbstractPorous structure Li[Ni1/3Co1/3Mn1/3]O2 has been synthesized via a facile carbonate co‐precipitation method using Li2CO3 as template and lithium‐source. The physical and electrochemical properties of the materials were examined by many characterizations including TGA, XRD, SEM, EDS, TEM, BET, CV, EIS and galvanostatic charge‐discharge cycling. The results indicate that the as‐synthesized materials by this novel method own a well‐ordered layered structure α‐NaFeO2 [space group: R‐3m(166)], porous morphology, and an average primary particle size of about 150 nm. The porous material exhibits larger specific surface area and delivers a high initial capacity of 169.9 mAh·g−1 at 0.1 C (1 C=180 mA·g−1) between 2.7 and 4.3 V, and 126.4, 115.7 mAh·g−1 are still respectively reached at high rate of 10 C and 20 C. After 100 charge‐discharge cycles at 1 C, the capacity retention is 93.3%, indicating the excellent cycling stability.