Calcium copper titanate (CCTO) has been synthesized by high temperature solid‐state reaction from calcium carbonate, copper (II) oxide, and titanium dioxide as the starting materials. The formation and morphology of CCTO were confirmed by X‐ray diffraction, Fourier‐transformed infrared spectrophotometry, scanning electron microscopy (SEM), and particle size analysis. In order to develop flexible dielectric materials, acrylonitrile‐butadiene rubber (NBR)‐based composites were prepared with CCTO content varied from 0 to 120 phr (parts per hundred rubber). The cure characteristics of composites were assessed. High‐dielectric constant CCTO particles were blended into NBR to make composites with improved dielectric constant. Results showed that the NBR/CCTO composites had a high dielectric constant (10–20) with low dielectric loss (<0.4) and low conductivity (<10−3 μS/cm) at frequencies up to 106 Hz. However, the higher CCTO loadings had agglomeration in the NBR matrix, and thus tensile strength and elongation at break sharply deteriorated due to poor rubber‐filler interactions. The results showed lower storage modulus E′ and a reduction in Tg with the incorporation of CCTO in NBR matrix. Moreover, improved thermal stability of the NBR/CCTO composites was achieved. SEM was used to observe the dispersion of CCTO particles in NBR matrix.