A carboxy modified long-chain diol (CMLCD) was synthesized for the first time through esterification of pyromellitic dianhydride (PMDA) and polytetramethylene glycol 1000 (PTMG1000). Waterborne polyurethane (WPU) was prepared based on an organic solvent-free and self-catalytic process, using synthesized CMLCD as a hydrophilic diol. The CMLCD has self-catalytic ability to the reaction of hydroxyl and isocyanate during the prepolymerization, which can greatly shorten the preparation period and avoid the utilization of highly toxic catalyst such as dibutyltin dilaurate. Importantly, the prepared WPU has narrow particle size distribution with the average particle size of 137 nm, which leads to good stability even centrifugated at 3000 rpm. Mechanical test results show that the WPU film possesses good mechanical performance with the tensile strength of 59.3 MPa and elongation at break of 819.2%. Additionally, the prepared WPU film has high water resistance. This study is attractive for future green WPU in industrial production and application. (C) 2018 Elsevier Ltd. All rights reserved.