Electrocrystallization from solutions of the dissymmetrical ET derivative cyanobenzene-ethylenedithio-tetrathiafulvalene (CNB-EDT-TTF) in the presence of triiodide I-3(-) affords two different polymorphs (beta '' and kappa) with the composition (CNB-EDT-TTF)(4)I-3, both with a bilayer structure of the donors. These polymorphs differ in the packing patterns (beta ''- and kappa-type) of the donor molecules in each layer, in both cases with bifurcated C-N center dot center dot center dot H interactions effectively coupling head-to-head donor molecules, between layer pairs. Two beta '' polymorphs can be obtained with different degrees of anionic ordering. In one disordered phase, beta ''(d), with a smaller unit cell, the triiodide anions are disordered over two possible positions in a channel between the donor bilayers, while in the ordered phase, beta ''(o), the triiodide anions occupy only one of those positions in this channel, leading to the doubling of the unit cell in the layer plane. These results for beta '' phases contrast with the kappa polymorph previously reported, for which weaker disorder of the triiodide anions, over two possible orientations with 94 and 6% occupation factors, was observed. While the beta '' polymorphs remains metallic down to 1.5 K with a rho(300K)/rho(4x) resistivity ratio of 250, the kappa polymorph presents, a much smaller resistivity ratio in the range of 4-10 and superconductivity with an onset temperature of 3.5 K.