A first-principles density functional theory (DFT) study of [Formula: see text]-(BEDT-TTF)2X molecular conductors with X = I3, CsCo(SCN)4 (ambient pressure, 7.5 kbar and 10 kbar), CsZn(SCN)4, TlCo(SCN)4, RbCo(SCN)4 and RbZn(SCN)4 (220 K and 90 K) is reported. It is shown that these salts exhibit three different types of band structure each of them associated with a different physical behavior. In contrast with previous proposals it is found that the key electronic parameter behind the differences in the band structures is the intrastack transfer integral, t c . A new mechanism for the metal to insulator transition in the [Formula: see text]-(BEDT-TTF)2MM'(SCN)4 ([Formula: see text], Tl; [Formula: see text], Co) salts is proposed, where an order-disorder structural transition of the ethylenedithio groups doubling the periodicity along the stack direction drives the system into an electronically pseudo-1D system along the interstack direction that is subject to a 4k F charge localization of holes. The structural rearrangement is such that the holes are not distributed equally between the two donors; the larger hole density is associated with the B donors which establish the strongest hydrogen bonds with the anion layers. A detailed microscopic description of how disorder of the ethylenedithio groups, the θ dihedral angle and the electronic structure intermingle and lead to the unusual phase diagram of these salts is presented. In this framework the role of pressure and uniaxial strain in controlling the physical behavior of these salts is discussed.