We studied laser ablation and plasma property evolution for a nickel (Ni) doped tin (Sn) oxide nanostructures target using laser-induced breakdown spectroscopy (LIBS). The transition metal Ni doped tin oxide nanostructures were synthesized by co-precipitation and hydrothermal methodologies. The size of prepared nanoparticles was verified by X-ray diffraction and transmission electron microscopy techniques. A frequency-doubled pulsed Nd:YAG laser with a wavelength of 532 nm was used to produce ablated plasma nanostructures. Ablation of doped and undoped nanostructures revealed salient-enhanced spectral emissions compared with their bulky counterparts. The emission lines of the constituent elements of doped material were used to find plasma parameters. The plasma temperature was estimated from a Boltzmann plot, and the electron number density was determined from the Saha-Boltzmann equation. The self-absorption effect has been observed in tiny plasma of nanostructures. The affected profiles of spectral lines of Ni and Sn nanoparticles due to self-absorption in LIBS spectra were corrected by the internal reference self-absorption correction (IRSAC) methodology. After correction of emitted line intensities by IRSAC, the electron number density (END) conservation approach was applied for quantitative analysis of doped nanostructures. In the END conservation approach, quantitative analysis of samples was carried out using electron number densities. Quantitative results derived from the END conservation approach at high and low concentrations exhibited good correlation when these were compared and validated with results from a conventional calibration free approach and the standard recognized energy dispersive X-ray technique.