Abstract The experimental NMR relaxation study of Xe-131 dissolved in 1,3-dioxane and 1,4-dioxane indicates that the intermolecular quadrupole relaxation mechanism is equally as efficient in both solvents even if 1,3-dioxane is a dipolar molecule while 1,4-dioxane is not. In order to interpret this observation, molecular-dynamics simulations were performed for model systems of xenon gas dissolved in 1,3-dioxane and 1,4-dioxane. The simulations were able to satisfactorily reproduce various experimental data for each system and, in perfect agreement with the experiment, yielded the same 131Xe quadrupole relaxation rate in both solvents. This result was obtained assuming an electrostatic origin of the electric-field gradient, and therefore validates this explanation. In 1,4-dioxane, the overwhelming part of the fluctuating electric-field gradient experienced by the xenon nucleus is due to the quadrupole moment of the solvent molecules. In 1,3-dioxane, the dipole moment is responsible for approximately half the value of the amplitude of the electric-field-gradient fluctuations only. Contributions at least up to the octopole moment are important and, consequently, the correlation time characterizing the electric-field-gradient fluctuations in 1,3-dioxane is significantly shorter than the dipolar correlation time and is found to be similar to the correlation time value in 1,4-dioxane. The relaxation rate of 131Xe in dioxanes is compared to the value in other solvents including cyclohexane, and comments are made on the general concept of polarity.