In this paper, the investigation on the structure and molecular interactions in the binary systems containing aniline and 1-alkanol (1-pentanol up to 1-decanol) was performed in the framework of Kirkwood-Buff (KB) integrals and experimental techniques. The interpretation of obtained parameters shows that in binary mixtures with shorter chain alcohols, unlike molecules tend to form strong interactions, while increasing in the carbon atom of 1-alkanols reduces the strength of bonds and tendency of the heterogeneous molecules to stay along side. Mixtures structure was studied using the concentration-concentration structure factor, SCCð0Þ. Results from the application of this parameter show that the heterocoordination occurs in solutions involving 1-pentanol up to 1-heptanol, while for mixtures containing 1-octanol to 1-decanol, homocoordination is predominant. Also, the chemical short-range order parameter, α′which is an important function to understand the complex formation and phase segregation in the liquid mixtures was obtained and discussed for mentioned mixtures.