Tri-O-benzyl cellulose, tri-O-p-fluorobenzyl cellulose, and a corresponding series of cellulose mixed benzyl ethers were synthesized and blended with poly(epsilon-caprolactone) (PCL). Mechanical and thermal analyses indicated that none of the cellulose benzyl ethers or the cellulose mixed benzyl ethers was miscible with PCL. However, there was evidence of a limited degree of compatibility that exhibited a dependence on the substituent ratio, or copolymer composition, of the cellulose mixed benzyl ethers. The weak interactions in these blends were found to be nonspecific, and thus the limited compatibility is thought to arise from intramolecular interactions within the cellulose mixed benzyl ethers. The treatment of cellulose mixed derivatives as copolymers and the potential use of intramolecular effects in cellulose derivative blending is discussed.