Two low‐firing BiMVO5 (M = Ca, Mg) ceramics were prepared in the sintering temperature range of 760‐850°C. Their differences in phase formation, sintering behavior, and dielectric performances were investigated. BiCaVO5 formed a single phase with an orthorhombic structure, while BiMgVO5 crystallized in a monoclinic structure that needs longer dwelling time to obtain single phase. The optimized microwave dielectric properties were obtained with εr = 15.70, Q × f = 55 000 GHz (at 10.6 GHz), and τf = −71 ppm/°C for BiCaVO5, εr = 18.55, Q × f = 86 860 GHz (at 9.63 GHz), and τf = −65 ppm/°C for BiMgVO5. In addition, the large negative τf values of BiMVO5 (M = Ca, Mg) ceramics were successfully adjusted by forming composite ceramics with CaTiO3 and near‐zero τf values of +2 ppm/°C and −3 ppm/°C were obtained in 0.92BiCaVO5‐0.08CaTiO3 and 0.94BiMgVO5‐0.06CaTiO3, respectively. Both ceramics exhibited good chemical compatibility with Ag electrode. The results demonstrate BiMVO5 (M = Ca, Mg) ceramics to be attractive candidates in LTCC technology.