Synthesis of nanoscale TiO2 exhibiting specific properties of electron or ion conductivity is critical to improve the performance of dye solar cells (DSC). This paper presents the modified polyol-mediated synthesis of doped TiO2 nanoparticles. TiO2 samples were doped with cobalt (Co) and nickel (Ni) and the effects of calcination temperature (550 °C and 650 °C) on the crystallinity of pure samples were investigated. X-ray diffraction (XRD) analysis was used to determine the effect of dopant in lattice structure. The morphology and Crystal structure of TiO2 samples and their chemical analysis was conducted using scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectrometer respectively. Results show agglomeration of spherical particles in all doped samples. Crystal structure in the doped samples reveals modified phases and major crystal phase identical to anatase. It is observed that the molar ratio of water to metal can control the nucleation and growth and prevents significant agglomeration of nanoparticles. More effective doping was recorded for samples with 0.5 concentration. Effective hydroxyl group is detected in both 0.5 Ni and Co promising good photocatalytic material. SEM images of 0.2 Ni-doped sample shows smallest average particle size. © (2014) Trans Tech Publications, Switzerland.