Recently, there has been considerable interest in studying nanostructural properties of Bismuth (Bi) as a good electrode of electro-analysis, shape–memory alloys and photo-typical multiferric devices. We have thus demonstrated a series of experiments to synthesis Bi and BiFeO3 (BFO) nanoparticles using sol–gel method at ambient pressure and study their nanostructural properties using tapping mode of atomic force microscopy (AFM) and X-ray diffraction (XRD) techniques. These techniques lend themselves very well to investigate the structure of nanoparticles and to map out properties and structure on surfaces of Bi and multiferroic BFO. The present work shows that, all nanoparticles are crystallized by annealing at 500°C. The narrower and sharper peaks in 10% Bi respect to 15% Bi in BFO, indicate the compositional changes of BFO. High purity BFO-phase powders with particle size of about 70 nm have been successfully synthesized by the sol–gel process, followed by leaching in diluted nitric acid. Key words: Bismuth, nanoparticles, X-ray diffraction (XRD), atomic force microscopy (AFM) techniques.