Microwave dielectric properties of Li-containing orthorhombic compounds with the composition of MLi 2 Ti 6 O 14 (M = Ba and Sr) were investigated. The ceramics were synthesized by the conventional solid-state reaction route. The optimized sintering temperatures for the BaLi 2 Ti 6 O 14 and SrLi 2 Ti 6 O 14 ceramics are 1025°C and 1000°C, respectively. Favorable microwave dielectric properties were obtained with moderate e r of 31.7 and 33.6, quality factor Q 3 f values of 23 300 (at 7.3 GHz) and 8700 GHz (at 6.8 GHz), and low-temperature coefficient of resonant frequency (s f ) values of -15.4 and -2.7 ppm/°C for BaLi 2 Ti 6 O 14 and SrLi 2 Ti 6 O 14 ceramics, respectively. The addition of BaCu(B 2 O 5 ) can effectively reduce the sintering temperature below 930°C without degrading the microwave dielectric properties. Compatibility with Ag electrode indicates these materials could be applied to low-temperature cofired ceramic devices.