||Four different sets of starting powders (1) Al4C3, Ti, C, (2) Al4C3, Ti, (3) TiC, Ti, Al, (4) Ti, Al, C were adopted as starting powders to try to synthesize MAX phase Ti3AlC2 powders by mechanical milling and thermal annealing technique in this study. The milling time was set to be 4, 9 and 15 hours, and the annealing temperature was set to be 1200 C. The formation mechanism, morphological features and particle sizes of the processed powders resulting from different sets of starting powders were characterized and compared by X-ray diffraction analysis, scanning electron microscopic observation, and particle size analysis using laser scattering particle size distribution analyzer. Experimental results showed that milling the second set of powders for up to 15 hours did not cause any reaction to occur between the powders and no new phase was formed. For the rest three sets of starting powders, small amount of Ti3AlC2 phase and large number of TiC powder were generated after the milling. It was inferred from the processing of ball milling that Ti will first react with C to form TiC phase, which then reacts with Al to form Ti3AlC2 phase. All these milled powders were annealed at temperature of 1200 C for 2 hours, and the milled powders following this annealing treatment transformed more or less into Ti3AlC2 phase, wherein the fourth set of powders (Ti, Al, C powders) after the 9-hr milling and subsequent annealing treatment generated the most amount of Ti3AlC2 powder. After the thermal annealing treatment, the average particle size increases.