Driven by the urgent demand of detecting trace amounts of pentachlorophenol (PCP) in contaminative water, a label-free immunosensor with ultra sensitivity and high selectivity was constructed based on a hybrid CdSe(x)Te(1-x) (0 ≤ x ≤ 1) nanocrystal (NCs)-modified TiO(2) nanotube (NT) arrays for the first time. The CdSe(x)Te(1-x) NCs were photoelectrodeposited on inner and outer space of the TiO(2) NTs, leading to high photoelectrical conversion efficiency in the visible region. PCP antibodies are covalently conjugated on the TiO(2) NTs due to the large surface area and good biocompatibility. Since the photocurrent is highly dependent on the TiO(2) surface properties, the specific interaction between PCP and the antibodies results in a sensitive change in the photocurrent, with a limit of detection (LOD) of 1 pM. High sensor-to-sensor reproducibility is achieved. The sensor was applied for the direct analysis of river water samples.