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Well crystalline selenium nanoparticles having an optical band gap of 2.95 eV have been synthesized using oxalic acid. Microstructural parameters such as crystallite size, lattice strain, cell parameters, and unit cell volume are estimated from X-ray diffraction line profile analysis by Rietveld refinement technique. dc and ac transport properties of the nanoparticles in the temperature range 300 K ≤ T ≤ 390 K and frequency range 20 Hz ≤ f ≤ 2 MHz have also been studied. The values of dc activation energies in the low and high temperature regions are found to be 0.083 eV and 0.382 eV, respectively. The charge transport mechanism of the sample follows correlated barrier hopping (CBH) model and the calculated value of barrier height and relaxation time is 0.786 eV and 2.023 × 10-11 s, respectively, while grain boundary contribution being greater than the grain contribution. Considering metal electrode-semiconductor contact as a back-to-back Schottky diode device, analysis of the current-voltage and capacitance-voltage characteristics is done to extract the Schottky barrier heights, ideality parameters, built in voltage, and charge density. With ±40 V sweep the capacitance versus voltage characteristics of the sample shows hysteresis behavior which may be attributed to the presence of deep traps.