Highly efficient formation of poly(propylene carbonate) can be achieved in the coupling of CO2 and propylene oxide assisted by 4‐(N,N‐dimethylamino)pyridine (DMAP) and catalyzed with salen chromium(III) chloride by using DMAP/Cr ratios of less than 2. Under these conditions a possible backbiting mechanism is suppressed, leading to only minor amounts of cyclic carbonate as a side product.