In this research work, Influence of Fe and Ni dopant on structural Ba0.6Sr0.4TiO3 nanocrystalline was studied. The pure and (Fe and Ni)-doped Ba0.6Sr0.4TiO3 (Ba1-xSrxTiO3, where (x=0.4), Ba1-xSrxTi1-yFeyO3, where (x=0.4, y=0.1) and Ba1-xSrxTi1-yNiyO3, where (x=0.4, y=0.1)) in powder, abbreviated as (BST), (BSTF) and (BSTN), respectively were prepared by a modified Sol-gel technique. In this process, stoichiometric proportions of barium acetate and strontium acetate were dissolved in acetic acid and titanium (IV) isopropoxide was added to form BST gel. The as-formed gels were dried at 200°C and then calcined at 850°C for crystallization. In order to improved crystallization, surface morphology and optimized grain size used Fe+3 and Ni2+ ions. Samples were characterized by Infrared spectroscopy method (FT-IR), UV-Visible spectroscopy, X-Ray Diffraction technique (XRD), Field Emission Scanning Electron Microscope (FESEM) and Energy Dispersive X-Ray Spectroscopy (EDS). The Nano-scale presence and the formation of the cubic perovskite phase as well as the crystallinity were detected using the mentioned techniques. The results showed that, the adding Fe and Ni to BST structure lead to decrease of the average size of nanoparticles and change the optical properties of the BST. The nanocrystallite sizes obtained were nearly 38, 37 and 34 nm, for BST, BSTF and BSTN powders calcined at 850°C, respectively.