The poly(3-hydroxyoctanoate) (PHO) is a biodegradable polyester containing hydrophobic side chains. One way to obtain more hydrophilic polyester consisted in the introduction of polar groups in the side chains. Carboxyl groups (PHO75COOH25) were introduced by chemical modifications. The role of carboxyl groups was investigated in the first part as potential support for cell seeding by studying the cell adhesion and proliferation, and in the second part as potential drug carrier by comparing the abilities of PHO and PHO75COOH25 to form degradable particles. Measurements of human bladder RT112 cells adhesion were done with or without collagen IV. Adhesive RT112 cells were counted by a colorimetric MTT test. The results showed that the COOH pendant groups of PHO75COOH25 films promoted cell adhesion after 4 h of incubation. The proliferation of cells is not improved after 4 days of incubation because of a reorganization of macromolecular chains and reorientation of COOH groups. This surface restructuration when the film was in contact with water was showed by contact angle measurements. We showed that the presence of COOH groups modified the hydrophobic/hydrophilic balance and enhanced the formation of particles. Stable lyophilisable particles were then obtained with diblock copolymer P(HO75COOH25-b-CL); the caprolactone block (CL) was necessary to improve particles stability. The results showed that the release of doxorubicin from the particles is enhanced in presence of hydrophilic and degradable block (PHO75COOH25). It was possible to obtain a degradable functional polyester based on PHO with carboxyl pendant groups to improve degradation rate by simple hydrolysis required for drug delivery systems. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117: 1888-1896, 2010