In this study, the effect of particle size of fly ash (FA) on the interfacial interaction between the filler particles and the polymer matrix is investigated. Structural and physical characterization of FA with different particle sizes show that its chemical composition is highly dependent on the particle size. The mechanical, dynamic‐mechanical, structural, and microstructural properties of the composites are evaluated. Interfacial interaction between FA particles and the polymer matrix is assessed experimentally using a nanoindenter and numerically using two different models developed by Pukanszky and Kubat. The composites reinforced with smaller particles exhibit better mechanical, viscoelastic, and microstructural properties. Structural and interfacial studies show that, although the characterized amount of silicon oxide in the small particles is lower than the large particles, the concentration of –OH group in SiO₂ is particle‐size and surface‐area dependent. Therefore, smaller particle inclusions result in better interfacial interaction and improved properties. This observation is consistent with the numerically estimated interfacial interaction. J. VINYL ADDIT. TECHNOL., 25:134–143, 2019. © 2018 Society of Plastics Engineers