The barbital (Bar) is one of the barbituric acid derivatives. It possesses a potent sedative-hypnotic property. Structural, thermal and morphological properties of the charge transfer (CT) products obtained from the reaction of barbital (Bar) with chloranilic acid (CLA), chloranil (CHL), TCNQ and DBQ π-acceptors were reported. The products were prepared in methanol media, isolated and fully characterized spectroscopically, thermally andmorphologically using IR, 1H NMR, Raman, UV–Vis., TG, XRD and SEMtechniques. Experimental results obtained by spectroscopic titrations and elemental analysis suggested that the reaction stoichiometry is 1:1, and the synthesized productswere [(Bar)(CLA)], [(Bar)(CHL)], [(Bar)(TCNQ)], and [(Bar)(DBQ)]. The complexation of Bar with CHL, TCNQ and DBQ acceptor was taking place through n → π* interaction, while its complexation with CLA acceptor was taking place by the formation of intermolecular hydrogen bond. Formation of the productswas thermally stable as indicated by the TG analysis. SEM and XRD analyses indicate that the products possess uniformmicrostructureswith well-organized nano-sized particles having a main diameter in the range around ~50 nm.