Willemite ceramics (Zn2SiO4) possess excellent millimeter-wave dielectric properties, but it also has a high sintering temperature above 1300°C by traditional solid-state reaction and relatively large negative τf value. Zn2SiO4 nanoparticles synthesized by Sol–Gel method were used to improve the sintering and dielectric properties of the Zn2SiO4 ceramics. Using the nanoparticles, Zn2SiO4 ceramics can be sintered at a low temperature, 1150°C and exhibited improved microwave dielectric properties of εr =6.62, Q × f=24500 GHz, τf =-59ppm/°C. By adding TiO2 with high positive τf value (+450 ppm/°C) and CuO as sintering aid, near zero τf value and low sintering temperature can be achieved. With 11wt% of TiO2 and 5 wt% of CuO, an εr value of 9.3, a Q × f value of 12200GHz and a τf value of -11 ppm/°C were obtained at 1000°C, confirming the promising potential of the CuO-added TiO2-Zn2SiO4 ceramics as candidate materials for low–temperature cofired ceramic (LTCC) devices.