We prepared a series of Gd2O3:Yb,Er,Ca (3/1/xmol.%, x represents the nominal concentration of Ca element including 0, 2, 3, 4, 5, 7, 10) upconversion nanoparticles (UCNPs) with regular morphology via a wet-chemical route. We observed a simultaneous enhancement of upconversion luminescence (UCL) emission of Gd2O3:Yb,Er after Ca2+ ions were doped. When the doping level of Ca2+ reaches its optimal concentrate at 5mol.%, the red and green emissions increased by 6.3 and 11 times, respectively. The potential application of Gd2O3:Yb,Er,Ca material as a noninvasion optical thermometry based on FIR technique was investigated. The sensing of temperature at both high and room temperatures was realized by choosing different parameters. The absolute temperature sensitivity (S′a) of Gd2O3:Yb,Er nanoparticles at 293K reached 0.0875K−1, whereas Gd2O3:Yb,Er, 5mol.%Ca was chosen as sensor of high temperature due to its considerable Sa of 0.0060K−1 at 573K. The resultant UCNPs provided a new way for sensitive thermal detection at various target temperatures.