The charge-transfer complexes of formula D(TCNQ)2 are formed between pi-acceptor TCNQ (7,7',8,8'-tetracyanoquinodimethane) and phenolic donors such as p-aminophenol, alpha-naphthol, 2,4,5-trichlorophenol, and p-cresol. Solution growth and an electrochemical method were used to synthesize the complexes. Their structural analyses were performed using elemental analysis (C, H, N, and halogen), X-ray diffraction =D) patterns, scanning electron microscope (SEM) photographs, dc electrical conductivity, and spectral properties (electronic and H-1 NMR), which reveals that these quasi-one-dimensional monoclinic crystalline compounds are synthesized in the single phase with space group P-2/(1/n) and are of semiconductor nature at room temperature. The stoichiometric ratio of donor and acceptor in the complex D(TCNQ)(2) is found to be in a 1:2 ratio, respectively.