The role of capping ligand concentration on the microstructural characteristics of strontium titanate (SrTiO₃ or STO) nanoparticles has been investigated. Capping the surface of primary particles with ligand having long alkyl chain protects the increase in nanoparticle size by hindering the agglomeration. Therefore, in the present work the role of ligands namely cetyltrimethyl ammonium bromide (CTAB) and polyvinylpyrrolidone (PVP) on the structure and surface morphology of STO have been studied by varying their concentrations from 0.01 to 0.08 M and 0.001 to 0.008 M respectively. The structure of STO was determined using the X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. The surface morphologies of the different STO samples were viewed through the field emission scanning electron microscopy (FESEM). A cubic crystalline phase formation of STO has been observed as revealed from the XRD and TEM images. The typical crystallite size, strain and dislocation density determined for PVP capped STO are 29 nm, 2.08 × 10⁻⁰³ and 1.194 × 10¹⁵ m⁻², respectively. FESEM images manifested a decrease in the grain size as a result of increase in the concentration of CTAB to 0.05 M and PVP to 0.005 M. Nearly spherical grains with some sort of fusing have been observed at lower and higher concentrations of the CTAB and PVP in both the cases.