High temperature sensing sensitivity and luminescence intensity of phosphors are crucial factors for excellent optical temperature sensing performance. Based on material design, the pure phase and two-phase solid solutions were prepared by regulating the relative content of cations Ca2+ and La3+ in CaWO4–La2(WO4)3, respectively. The up-conversion luminescence (UCL) and optical temperature sensing performance of rare earth ions Er3+/Yb3+ co-doped CaWO4–La2(WO4)3 were studied. As guided by regulating cation composition through partial substituting Ca2+ ions by La3+ ions, the UCL intensity of two-phase solid solutions at 552 nm is much higher than that of pure phase material. The UCL intensity of 0.2La2(WO4)3–0.8CaWO4: 1%Er3+, 5%Yb3+ is as 33.5 times as that of CaWO4: 1%Er3+, 5%Yb3+ material. More importantly, the high temperature sensing sensitivity (0.01026 K−1) is achieved in a wider temperature range 83–683 K in optimal UCL material 0.2La2(WO4)3–0.8CaWO4: 1%Er3+, 5%Yb3+. It is suggested that material design theory can be used as a powerful tool to accelerate discovery of novel optical temperature sensing materials, with implications even for the design of other optoelectronic materials.