The regularities of the donor‐acceptor interaction of nucleic acid bases and some of their derivatives with the strong acceptor 7,7,8,8‐tetracyanoquinodimethane (TCNQ) in thin amorphous films at 77 K were studied using UV and visible spectroscopy. Purine and pyrimidine bases are shown to form charge transfer TCNQ complexes whose band energies hνct = Ip − EA − (H* − H0) are linearly dependent of the donor ionization potential Ip. Calculated differences between the interaction energies of uncharged molecules and ion radicals, ΔE ≈ 3.0 eV, are in good agreement with experimental variations of the complex dissociation energies in the ground and excited states, (H* − H0) = 2.73 eV. Annealing of the films of complexes containing cytosine, 1‐methylcytosine, uracil, and caffeine leads to ordering of their structure and the formation of ion radical salts. Copyright © 1979 John Wiley & Sons, Inc.