The past few decades have witnessed an ever-growing scholarly interest in microwave dielectric ceramics with the rapid development of telecommunication. [1][2][3][4] Recently, there is a strong ongoing search for dielectric ceramics with a dielectric constant (ε r ) less than 15, a low dielectric loss (tan δ = 1/Q), and a near-zero temperature coefficient (τ f ) to meet the demands for microwave substrate applications. 5,6 Although traditional inorganic substrates such as Al 2 O 3 possess excellent dielectric properties, the exploration for novel materials with superior dielectric properties and sintering behaviors continues today.Pyrophosphates belong to typical low-permittivity compounds, in which M 2 P 2 O 7 possesses two kinds of structure according to the ionic radius of M that is a divalent cation. 7 The structure is recognized as thortveitite-type if the M ionic radius is less than 0.97 Å (M = Mn, Mg, Zn), while the structure converts to dichromate-type if the M ionic radius is larger than 0.97 Å (M = Ca, Sr, Ba). The dependence of dielectric properties on the phase composition of M 2 P 2 O 7 (M = Ca, Sr, Ba, Mn, Mg, Zn) was investigated by Bian et al. 8 and dielectric properties were ε r = 6.1~8.4, Qf = 12300~53500 GHz, and τ f = −23~−746 ppm/°C. Sutapun et al. 9 studied the substitution effect of Zn 2+ at the Mn site of Mn 2 P 2 O 7 , and found that the dopants of Zn 2 P 2 O 7 were diffused completely into the Mn 2 P 2 O 7 structure, forming solid solutions.In recent years, many compounds with the general formula of M2M1P 2 O 7 have been reported with excellent microwave dielectric properties and low sintering temperatures. Complex pyrophosphates compounds M2M1P 2 O 7 (M2 = Ca, Sr; M1 = Zn, Cu) were investigated as low temperature cofired ceramic (LTCC) materials due to their intrinsic low sintering temperatures. 10 In the past, the work of BaZnP 2 O 7 was mainly focused on the luminescence properties. 11,12 In 2016, Xie et al. 13 prepared BaZnP 2 O 7 ceramics through solid-state reaction and reported its dielectric properties: ε r = 8.4, Qf = 27925 GHz, and τ f = −56.7 ppm/°C. However, there are