ABSTRACTIn this study, we examined a facile approach for achieving a fine dispersion of barium titanate (BT) nanoparticles (NPs) in epoxy thermosets. First, the surfaces of BT NPs were modified with poly(ε‐caprolactone) (PCL) via a surface‐initiated ring‐opening polymerization approach. We found that the PCL‐grafted BT NPs were easily dispersed in epoxy thermosets. The fine dispersion of the PCL‐grafted BT NPs in the epoxy thermosets was evidenced by transmission electron microscopy and dynamic mechanical thermal analysis. We found that the organic–inorganic nanocomposites displayed significantly enhanced dielectric constants and low dielectric loss compared to the control epoxy. The nanocomposites containing 14.1 wt % BT NPs possessed dielectric constants as high as at a frequency of 103Hz. The dielectric loss was measured to be 0.002 at a frequency of 103Hz. The improved dielectric properties are accounted for the fine dispersion of the BT NPs in the epoxy thermosets. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43322.