A new technique to process ceramic/polymer grain boundary capacitors has been developed and demonstrated using BaTiO3 as the ceramic conducting phase and LaRC-TPI polymer as the insulating phase. The particles were characterized by transmission electron microscopy and the dielectric properties of the capacitors were measured at room temperature and 100 kHz. The overall best composite grain boundary capacitor was made with 40 vol% polymer after milling the powder for 1 h. It had a dielectric constant of 58 and a dielectric loss of 0.01. The dielectric properties of the grain boundary capacitors could be manipulated by changing processing variables such as milling time and volume fraction of polymer.