Ester interchange, alcoholysis, and acidolysis of polypivalolactone (PPVL) were studied by melting PPVL with bisphenol diacetates, 1, 4-butanediol, or aromatic diacids. Interchange of PPVL with the diacetates and the diol occured readily, in particular in the presence of a titanium catalyst. Melting PPVL with 10 mol-% of bisphenol-Adiacetate in the presence of 0,5 wt.% tetrabutylorthotitanate resulted in an incorporation of 33% of the diacetate in the polymer chains, whereas the logarithmic viscosity number decreased by 81%. The ester interchange was suggested to proceed by an initial cleavage of ester bonds in the polymer chain of PPVL, resulting in the formation of shorter chains, followed by a reaction between the newly formed ester end-groups and initially present hydroxyl chain ends. The acidolysis of PPVL with the diacids proved to be less effective; in the case of the acidolysis of PPVL with 10 mol-% isophthalic acid, less than 1% of the diacid was incorporated in the polymer chains and a decrease in the logarithmic viscosity number of only 22% was found. Both the high stability of the ester bond in PPVL towards acids in general and the heterogeneity of these systems were supposed to cause the behaviour of PPVL with respect to acidolysis. The results concerning the interchange reactions with PPVL were compared with studies on other polyesters.