Barium titanate material systems are the basic microwave dielectrics attracting particular interests and subject to many researches due to lots of intriguing properties, such as, its high temperature stability, low loss, high dielectric constant etc. at microwave range. However, BaTi4O9 and Ba2Ti9O20 ceramics usually need very high sintering temperatures (∼1300°C and above) to achieve sufficient density. The present work attempts to investigate the microstructures and corresponding electric properties of low temperature co-fired BaTi4O9 microwave dielectric ceramics with copper electrode and B-Si-Ba-Zn-O glass in reducing atmosphere. Experimental results show that specimens of BaTi4O9 ceramics with various glass compositions and Cu-electrode exhibit different colors and can be attributed to glass diffusivity and reaction with Cu element during sintering. Glass composition plays an important role of the mass transportation of glass. B2O3/SiO2 ratio determines glass viscosity and BaO/ZnO ratio contributes to wettability of glass with BaTi4O9 ceramics. In x-ray diffraction patterns, we can observe different Ba-Ti-O phases with various Ba/Ti ratio. Ba4Ti13O30 may form when the BaO content in glass is too high (BaO/ZnO ratio is greater than 2). Instead, the BaTi6O13 appears as the content of BaO is low, such as BaO/ZnO ratio is smaller than 0.75. Both extreme conditions degrade the electrical properties of materials. Appropriate composition of glass not only improves material density during sintering, but also enhances phase stability of dielectrics and electrical properties.