A series of novel miktoarm star polymers composed of a poly(ethylene oxide) (PEO) and two side-chain liquid crystalline azobenzene-containing polymethacrylate (PEO-(PMMAZO)(2)) were prepared using atom transfer radical polymerization (ATRP). Bifunctional macroinitiator PEO-Br-2 was synthesized by C-13 NMR and IR. Kinetic study showed that it was a first order reaction referred to the monomer MMAZO, namely, 6-(4-methoxy-4'-oxy-azobenzene)hexyl methacrylate. The liquid crystalline behaviors of the miktoarm star polymers were studied by differential scanning calorimetry (DSC) and polarized optical microscope (POM). They exhibited smectic and nematic mesophases when Mn was beyond 9.4x10(3) g/mol. The phase transition temperatures of the smectic and nematic phases increased while the melting temperature of PEO decreased with increasing molecular weight of the LC block. Compared with diblock polymer PEO-PMMAZO, the melting temperature of PEO in miktoarm star polymer decreased more rapidly.