The electronic structure of the gold nanoparticles were investigated by semi-empirical Wolfsberg–Helmholz method. This is a variant of the molecular orbitals method. Molecular orbitals are represented as a linear combination of valence atomic orbitals of the atoms of the nanoparticle. As the atomic orbitals used 6s-, 6p_y, 6p_z and 6p_x Slater atomic orbitals of gold atoms. The exponential parameters of Slater functions were calculated and defined the analytic expression of the basis functions. The numerical values of the unknown coefficients of the linear combination are found by solution of equations of molecular orbitals method. Calculations were carried out with own computer program. The orbital energies, potential ionization, the total electronic energy and effective charge of atoms of gold nanoparticles were calculated. The results indicate that the gold nanoparticles are soft, electrophile and conductive material.