Novel aliphatic, random copolyesters, containing co‐units derived from a poly(alkylene dicarboxylate) and a poly(butylene 1,4‐cyclohexanedicarboxylate), have been synthesized and characterized in terms of molecular structure and thermal properties. In particular, the effects of the molar composition, the length of the aliphatic sequences, and the cis/trans ratio of the 1,4‐cyclohexylene units on the characteristics of the crystalline and amorphous phases are discussed. Some interesting structure‐property relationships have been found. The materials result to be very promising new biopolymers as they are characterized by a potential biodegradability and good physical properties, which can be easily modified, according to the requests of specific applications, by little changes in the molecular structure.magnified image