Double-perovskite phosphors exhibit unusual thermal and luminescent behavior and could potentially be applied as efficient and sensitive luminescent temperature sensors. Four double perovskite hosts─Ba2MgMoO6 (BMM), Sr2MgMoO6 (SMM), Ba2ZnMoO6 (BZM), and Sr2ZnMoO6 (SZM)─are studied for the correlations between the symmetry, energetic structure, luminescence, and thermometric performance. The quantum yield of Eu3+ emission in those hosts is higher for the samples with high cubic symmetry and ranges up to over 20% for Ba2MgMoO6. The Eu3+ ions can be excited indirectly by the host absorption bands in the UV and charge transfer band (CTB) in the blue range. The symmetry of the host plays a crucial role in the thermal stability of the host emission, which together with varying activation energy of Eu3+ luminescence provides a basis for thermometric sensitivity optimization. The relative sensitivities (Sr) obtained by the Eu-doped molybdenite hosts are 3.2% at 75 °C for Sr2MgMoO6 and 9.2% at −196 °C for Ba2ZnMoO6. It is also demonstrated that the sensing performance is higher in hosts with a uniform quenching profile of host luminescence and steep quenching of Eu3+ luminescence.