Dielectric constants of the binary mixtures of acetophenone,p-chloroaceto-phenone,p-methylacetophenone ando-hydroxyacetophenone in dilute solutions of benzene and 1,4-dioxane were measured at 303 K and at frequency 100 kHz. The low frequency molecular dynamics of acetophenone and its derivatives have been studied by evaluating the Kirkwood correlation factorg, molar polarizationP2, excess correlation factor δg and excess free energy ΔG. The dipolar contribution to excess free energy of mixing arising from long-range electrostatic interaction and short-range interaction between identical molecules has been assessed separately. The presence of α- and β-multimers in the above systems was identified. The results have been used to interpret the fluid structure in such mixtures.