Li1·2(Mn0·53Co0.27)O2 cathode material was successfully synthesized using a microwave sintering method. The as-prepared material remained in an octahedral shape after sintering at 800 °C with a rapid heating rate of 35 °C min−1. The as-prepared sample was demonstrated to have better electrochemical performance than that synthesized using a conventional method. The enhanced electrochemical performance can be ascribed to the minor change in material morphology and less particle agglomeration in the macroscopic scale, which depends on the rapid-sintering mechanism provided by microwave sintering. The rapid-sintering mechanism was studied in an in-situ transmission electron microscopy (TEM) heating experiment, which directly presented the crystal growth process and the evidence for the morphological damage of Li1·2(Mn0·53Co0.27)O2 materials at approximately 830 °C.