Microwave dielectric ceramics have played an important role in modern wireless communication systems, such as resonators, capacitors, and filters. 1-3 With the increase in communication frequency, microwave dielectric ceramics with low permittivity (ε r < 15), high-quality factor (Q × f), and near-zero temperature coefficient of resonant frequency (-10 ppm/°C ≤ τ f ≤ +10 ppm/°C) have attracted the attention of many researchers. Microwave dielectric ceramics with low ε r and high Q × f values mainly include: silicates, 2-8 germanates, 9-13 vanadates, 14-18 and stannates. 19-25 The Q × f value of stannates (Ca 2 SnO 4 19 and Li 2 O-MgO-SnO 2 24,25) exceed 100,000 GHz, and high Q × f value is necessary to improve frequency selectivity. We first reported the Ca 2 SnO 4 ceramic with excellent microwave dielectric properties (ε r = 9.9, Q × f = 120,100 GHz, and τ f =-45.6 ppm/°C). 19 The Ca 2 SnO 4 ceramic exhibited orthorhombic crystal with Pbam space group, and the CaSnO 3 phase always existed in the preparation of Ca 2 SnO 4 ceramic through stoichiometric composition. The CaSnO 3 phase can be prioritized for synthesis in the CaO-SnO 2 system. However, the cylindrical CaSnO 3 ceramic could not be obtained through traditional solid-state reaction because of a