A novel dinaphthodioxocin-containing diol monomer, 8,16-methano-16H-dinaphtho[2,1-d:1',2'-g][1,3] dioxocin-2,14-diol (MDDD) was synthesized in high yield and purity through the condensation of 2,7-dihydroxy-naphthalene with malonaldehydetetramethyl acetal at room temperature. It is used as a new monomer for the synthesis of a series of novel dinaphthodioxocin-containing aliphatic polyesters by interfacial polycondensation method. The new diol monomer was fully characterized by IR, NMR, mass spectroscopies, and elemental analysis. Optimal conditions for polyesterification were obtained via study of the model compounds. Polyesters derived from MDDD and four aliphatic diacid chlorides had inherent viscosities ranging from 0.26 to 0.38 dL/g. The chemical structure of the polymers was fully characterized by IR, NMR spectroscopies, and elemental analysis. The physical properties of the polymers were studied. All the new polymers show good thermal stability and very good solubility in most organic solvents. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 120: 3357-3362, 2011