FTIR spectral measurements have been carried out on the binary solutions of ethanol with 1,4-dioxane at the compositions 0.2:0.8, 0.4:0.6, 0.6:0.4, 0.8:0.2 (mole fraction of ethanol: mole fraction of 1,4-dioxane) at room temperature. There seems to be no change in the geometry of the open polymeric forms of ethanol in the presence of 1,4-dioxane. (ethanol)O-H center dot center dot center dot O (1,4 dioxane), (ethanol methyl)C-H center dot center dot center dot O (1,4 dioxane) and (1,4-dioxane)C-H center dot center dot center dot O (ethanol) heterointeractions coexist in the binary solutions. In 1,4-dioxane rich solutions, the dissociation of ethanol molecules is the dominant effect than the (ethanol)O-H center dot center dot center dot O (1,4 dioxane) heterointeraction. All the heterointeractions are weakened in ethanol rich solutions where the ethanol molecules tend to attain their higher order multimerization through their self association. NMR and UV-vis spectroscopic studies have been carried out on the system ethanol +1,4-dioxane. The change in the chemical shift positions of methylene and methyl carbon nuclei in the solution and the hyperchromism, bathochromism and hypsochromism observed in the UV-vis spectrum compliment the heterointeractions suggested by FTIR studies. (C) 2017 Elsevier B.V. All rights reserved.