Poly(lactic acid) (PLA) blends and composites were prepared from thermoplastic starch, poly(butylene-adipate-co-terephtalate), polycarbonate, wood flour and CaSO4 in a wide range of compositions. The thermal transitions of PLA were studied by differential scanning calorimetry. The detailed analysis of the transitions of PLA/thermoplastic starch blends indicated that they all are determined by the molecular mobility of PLA chains. Blending changes molecular mobility, and thus it often decreases glass transition temperature and modifies the extent of enthalpy relaxation. All other transitions and characteristics, i.e. cold crystallization, melting and the corresponding enthalpies, change accordingly. Increased molecular mobility accelerates also the physical ageing of the polymer. The interaction between PLA and the various components used for modification changed in a wide range, but no direct correlation was found between the strength of interaction and molecular mobility.