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When poly (lactic acid-co-melamine) [P(LA-co-MA)] is synthesized via direct melt polycondensation (DMP), with the more MA in the feed content, the copolymer with a three-MA-core structure linked by the ether bond is formed. Increasing the molar feed ratio n(LA)/n(MA), the structure of the copolymers is gradually changed from multi-core structure into SPLA structure only containing one MA core, and a peak value of Mw exists as expected. The aromatic cores with different functional groups have an important influence on the Mw peak value, and the internal factors are the conjugate effect and the nucleophilicity caused by the different functional groups themselves.