A model of the energy spectrum of holes near the edge of the valence band of Cu₂ZnSiSe₄ is proposed from investigations of the resistivity, q(T), in Cu₂ZnSiSe₄ single crystals. The Mott variable-range hopping (VRH) conductivity mechanism is established in the temperature interval of ∼100-200 K, whereas between ∼200 and 300 K, the conductivity is determined by thermal excitations of holes to the mobility edge of the joint energy spectrum of the overlapped acceptor and valence bands. Parameters of the localized holes and details of the density of states near the edge of the valence band are determined, including the relative acceptor concentration, N/Nc ≈ 0.41-0.49 (where Nc ≈ 7 × 10¹⁸ cm 3 is the critical concentration of the metal-insulator transition), the relative localization radius a/a_B ≈ 1.7-2.1 (where a_B 13.1 Å is the Bohr radius), the semi-width of the acceptor band, W≈ 95-106 meV, centered at the energy E₀ - ∼ 59 meV above the top of the valence band, the average density of the localized states (DOS), g_av - ∼ (1.4-1.8) × 10¹⁶ meV^-1 cm^-3 and the DOS at the Fermi level, g(μ) ≈ (4.1-5.4) × 10¹⁵ meV^-1 cm^-3.