A new series of CnDT-EDO-TTF [n=5, 6, 7, 8; (cis-1,2-cycloalkylene-1,2-dithio)ethylenedioxytetrathiafulvalene] donors containing cycloalkylene and ethylenedioxy groups as a source of intermolecular hydrogen bonds and the steric hindrance has been synthesized. The charge transfer (CT) salts, β''-(CnDT-EDO-TTF) 2 (PF 6 ) x (n=5, 6, 7, 8), have the similar β''-type donor arrangements owing to the intermolecular hydrogen-bonded network (CH...O) in the two-dimensional (2D) plane. The steric hindrance of cycloalkylene groups enlarges the intermolecular distance in the order from n=5, 6, 7, to 8 salt. The calculated bandwidth, however, decreases in the different order from n=8, 5, 7, to 6 salt in consideration of the 2D interactions. All salts, β''-(CnDT-EDO-TTF) 2 (PF 6 ) x , show a metallic feature down to 1.5K, and the temperature dependences indicate the negative chemical pressure effect from n=8, 5, 7, to 6 salt in the same order of the calculated bandwidth.