AbstractAccurate and high reciprocal resolution experimental structure factors of aluminum were determined from a synchrotron powder X-ray diffraction data measured at 30 K with sin θ/λ < 2.31 Å⁻¹. The structure factors have small deviations from independent atom model in sin θ/λ < 0.83 Å⁻¹. Theoretical structure factors were prepared using density functional theoretical calculations by full potential linearized augmented plane wave method. The deviation between experimental and theoretical data was also observed at around sin θ/λ ≈ 0.4 Å⁻¹. The charge density was determined by an extended Hansen-Coppens multipole modeling using experimental and theoretical structure factors. Charge density maxima at tetrahedral site were observed in both experimental and theoretical deformation density. The charge-density difference peaks indicating directional bonding formation were observed in the difference density between experiment and theory. The present study reveals tight binding like character of valence electron of aluminum. The fact will provide a crucial information for development of high-performance aluminum alloy.