Chiral molecular crystals built up by chiral molecules without inversion centers have attracted much interest owing to their versatile functionalities related to optical, magnetic, and electrical properties. However, there is a difficulty in chiral crystal growth due to the lack of symmetry. Therefore, we made the molecular design to introduce intermolecular hydrogen bonds in chiral crystals. Racemic and enantiopure bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) derivatives possessing hydroxymethyl groups as the source of hydrogen bonds were designed. The novel racemic trans-vic-(hydroxymethyl)(methyl)-BEDT-TTF 1, and racemic and enantiopure trans-vic-bis(hydroxymethyl)-BEDT-TTF 2 were synthesized. Moreover, the preparations, crystal structure analyses, and electrical resistivity measurements of the novel achiral charge transfer salt θ 21-[( S,S)- 2] 3[( R,R)- 2] 3(ClO 4) 2 and the chiral salt α’-[( R,R)- 2]ClO 4(H 2O) were carried out. In the former θ 21-[( S,S)- 2] 3[( R,R)- 2] 3(ClO 4) 2, there are two sets of three crystallographically independent donor molecules [( S,S)- 2] 2[( R,R)- 2] in a unit cell, where the two sets are related by an inversion center. The latter α’-[( R,R)- 2]ClO 4(H 2O) is the chiral salt with included solvent H 2O, which is not isostructural with the reported chiral salt α’-[( S,S)- 2]ClO 4 without H 2O, but has a similar donor arrangement. According to the molecular design by introduction of hydroxy groups and a ClO 4 − anion, many intermediate-strength intermolecular hydrogen bonds (2.6–3.0 Å) were observed in these crystals between electron donor molecules, anions, and included H 2O solvent, which improve the crystallinity and facilitate the extraction of physical properties. Both salts are semiconductors with relatively low resistivities at room temperature and activation energies of 1.2 ohm cm with E a = 86 meV for θ 21-[( S,S)- 2] 3[( R,R)- 2] 3(ClO 4) 2 and 0.6 ohm cm with E a = 140 meV for α'-[( R,R)- 2] 2ClO 4(H 2O), respectively. The variety of donor arrangements, θ 21 and two kinds of α’-types, and their electrical conductivities of charge transfer complexes based upon the racemic and enantiopure ( S,S)- 2, and ( R,R)- 2 donors originates not only from the chirality, but also the introduced intermolecular hydrogen bonds involving the hydroxymethyl groups, perchlorate anion, and the included solvent H 2O.