Blends of polypivalolactone (PPVL) with bisphenol‐A polycarbonate (PC) were studied. Physical PPVL/PC blends showed one Tg close to the Tg of 145 °C for PC, indicating immiscibility. Reactive blending of PPVL and PC with 0.5 wt.‐% tetrabutylorthotitanate was performed in diphenyl ether (260 °C) and in a twin screw extruder (TSE) at 280 °C. Based on the results from NMR, FT‐IR and thermal analysis, it was concluded that interchange reactions had occurred. The thermal properties indicated that, due to these interchange reactions, PPVL/PC blends had become more miscible. Although blending in a TSE was more efficient with respect to interchange reactions compared with blending in diphenyl ether, complete randomization was not observed.