The paramagnetic organic ions of the alkali+‐TCNQ− salts form linear chains. An analysis of the magnetic susceptibility of Li and Cu‐TCNQ shows that its variation with temperature can be exactly explained by one‐electron theory, leading to symmetrysplit ground state bands. The “pairing” in the chains at 0°K is due to the Peierls instability, while Adler Brooks crystallographic phase transitions (which can be first order or continuous) occur at higher temperatures in all alkali salts, except for LiTCNQ. The behavior of the magnetic susceptibility in these salts can be very well understood on the basis of one electron theory, when the pairing of the ions in the chains is allowed to vary with the temperature. Free energy calculations predict the order of the transition and the transition temperature very well. The transport properties, such as electrical conductivity cannot be explained by this simple model, because they are probably governed by disorder.