To obtain controllable and biocompatible drug carriers, a series of amphiphilic biodegradable multiblock polyurethanes end-capped by phosphorylcholine were designed and synthesized using L-lysine ethyl ester diisocyanate (LDI), poly(lactic acid)-poly(ethylene glycol)-poly(lactic acid) (PLA-PEG-PLA), 1,4-butanediol (BDO), and 4-hydroxy butyl phosphorylcholine (BPC) was used as end-capper to improve their biocompatibility and provide them with tailored micellization characteristics. The resulting polyurethanes were fully characterized with proton nuclear magnetic resonance spectroscopy (H-1 NMR), Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatograph (GPC), and differential scanning calorimetry (DSC). More importantly, these phosphorylcholine-capped polyurethanes can self assemble into micelles that are smaller than 100 nm in diameter. Their particle sizes, size distributions, and zeta potentials can also be tailored by varying the phosphorylcholine content. The incorporation of phosphorylcholine into these polyurethanes has significantly affected their degree of microphase separation, bulk and micelle degradation rates. This work provides a new and facile approach to prepare amphiphilic block copolymer micelles with controllable performances, which could be useful for drug delivery and bioimaging applications. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2033-2042, 2011