An amine-terminated hyperbranched poly(aryl-ether-urea) (HBPEU) was prepared from an AB2-type blocked isocyanate monomer and then its end groups were modified into urea (M-HBPEU) by reaction with phenyl isocyanate. Both of the polymers were doped with N3-dye along with KI/I2 to work as efficient polymer electrolytes in nanocrystalline dye sensitized solar cell. The increment in the conductivity of doped HBPEU and doped M-HBPEU was very significant and reached its value at 8.2 × 10−3 and 4.1 × 10−2 S/cm, respectively. The current–voltage (I–V) characteristics of these two doped polymers measured under simulated sunlight with AM 1.5 at 60 mW/cm2 generate photocurrent of 2.5 and 3.6 mA/cm2, together with a photo voltage of 690 and 750 mV, and fill factor of 0.55 and 0.61 yielding a overall energy conversion efficiency of 2.4% and 4.1%, respectively. These results suggest that M-HBPEU show better cell performance and conductance properties than the HBPEU. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40408.