The paper presents the results of studying the effects of droplet diameters on the NACA0012 airfoil ice accretion, which have been obtained in the 3D numerical simulation of icing. To simulate the motion of water droplets as a multiphase medium, the Eulerian approach is used, which assumes that water droplets have spherical shapes, do not undergo deformation and breakup, do not interact with each other, and that coalescence/fragmentation of droplets does not take place. Both monodisperse (of the same size) and polydisperse (of various sizes) droplets are considered; they are represented by the spectral Langmuir distributions. These spectral distributions take into account the polydisperse nature of droplets and provide a higher efficiency in predicting ice shapes. The obtained ice shapes on an airfoil are compared with the available experimental and calculated data. It should be noted according to the simulation results that the use of the standard size of droplet diameter equal to 20 μm does not allow for obtaining correct shapes of ice on the leading edge of the wing profile not at all temperature regimes. For temperatures from −20 °C to −10 °C, there is a noticeable difference compared to the experimental data. At the same time, for this temperature range, the use of the Langmuir spectral distribution of droplet diameters relative to 15 μm provides a better agreement of the formed ice forms with the experiment.