High molar mass poly(lactic acid) (PLA) is obtained by either the polycondensation of lactic acid or ring-opening polymerization (ROP) of the cyclic dimer 2,6-dimethyl-1,4-dioxane-2,5-dione, commonly referred to as dilactide or lactide (LA). This chapter describes preparation of polymers and copolymers of LAs with different structures, using polycondensation and ROP. Typical comonomers and polymers which are used for lactic acid or LA copolymerization include glycolic acid or glycolide, poly(ethylene glycol) or poly(ethylene oxide), and so on. PLAs having amino, carboxyl, or other functional groups are well reported in the literature. These functional groups can be utilized for chemical modification or as binding sites for biomolecules to impart selective binding and adhesion. PLA and its copolymers especially when used for biological applications, besides requirement of optimization of mechanical properties by engineering at the molecular level, also demands a fast degradation polymer rate.