Well-aligned ZnO nanowire arrays with a long length of more than 40 microm were prepared successfully by using the polyethylenimine (PEI)-assisted preheating hydrothermal method (PAPHT). Several important synthetic parameters such as PEI content, growth time, preheating time and zinc salt concentration were found to determine the growth of ultralong ZnO nanowire arrays, including length, diameter, density and alignment degree. The photoluminescence (PL) spectrum of as-grown ultralong ZnO nanowire arrays revealed a UV emission and a yellow emission, which was attributed to the absorbed hydroxyl group based on the peak shift after annealing in various atmospheres. The performance of dye-sensitized solar cells (DSSCs) increased with increasing length of ZnO nanowire arrays, which was mainly ascribed to the aggrandized photocurrent and reduced recombination loss according to electrochemical impedance spectroscopy (EIS). A maximum efficiency of 1.3% for a cell with a short-circuit current density (J(sc)) = 4.26 mA cm(2), open-circuit voltage (V(oc)) = 0.69 V and (fill factor) FF = 0.42 was achieved with a length of 40 microm.