Glass/ceramic composites applied in the field of low-temperature co-fired ceramics (LTCC) were successfully prepared at 670–710 °C by using waste soda-lime glass (WG) as a binder and natural volcanic ash as a ceramic raw material. Based on the theories of suppression and supplementary network effects, alkaline-earth metal ions (R2+, R = Mg, Ca, Sr, and Ba) and B2O3 were applied to improve the dielectric properties of WG and composites, respectively. The influence of R2+ on the crystal phase evolution, microstructure, mechanical, dielectric, and thermal properties of WG-volcanic ash-based composites were systematically investigated. By doping 2.5 wt% Ba2+ to the environment-friendly LTCC composites, physical properties i.e., εr of 4.86 at 1 MHz, tan δ of 6.32 × 10−3, coefficient of thermal expansion of 8.72 × 10−6/°C, and thermal conductivity of 1.04 W/(m·K) are obtained. It is worth mentioning that the environment-friendly LTCC composite uses WG with a low glass transition temperature to reduce the sintering temperature and a tiny amount of a modifier to adjust the dielectric performance instead of synthesizing specific crystals by adding lots of chemical reagents. These, in turn, do not only have the potential to be used in the LTCC packaging technology but also have significance for sustainable development. Additionally, because of good chemical compatibility between aluminum and the composites, the environment-friendly LTCC composites with ultra-low sintering temperature have the potential ability to lower the cost of LTCC packaging materials.