Through molecular designing, three poly(amic esters) (PAEs) have been synthesized from pyromellitic dianhydride (PMDA), 2,2'-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (BisAPAF), 4,4'-diaminodiphenyl ether (4,4'-ODA) and 2-hydroxyethyl methacrylate (HEMA). Due to the introduction of photosensitive acrylate groups and aqueous base soluble phenolic hydroxyl groups in the backbone, these poly(amic esters) can be used as the precursors of negative-working, aqueous base developable photosensitive polyimides (PSPIs). These poly(amic esters) were prepared by direct polymerization by using phenyl phosphonic dichloride (PPD) as an activator. The inherent viscosities of these polymers were 0.20 (dL/g). Their structures were characterized by Fourier transform infrared spectroscopy (FTIR) and H-1 NMR. In order to improve the photolithographic performance of these PSPIs, different photosensitizers, photoinitiators and a crosslinker have been added in the PSPI formulations. Among them, the Michler's ketone (MK)/tribromomethyl phenyl sulfone (TBPS) system gave the best results. Using a 2.38 wt% aqueous TMAH solution as a developer, patterns with a resolution of 10 mum were obtained from these PSPI formulations. In addition, the effects of the molecular structure of the precursors and the concentration of developer on the photosensitivity of the PSPI formulations were also discussed. (C) 2003 Elsevier Ltd. All rights reserved.