The size-dependent temperature sensitivity is observed on the upconversion luminescence of NaYF4:Er,Yb microspheres with sizes between 0.7 and 2 μm that are prepared by a poly(acrylic acid)-assisted hydrothermal process. It is found that the fluorescence intensity ratio (FIR) of their green upconversion emissions (with peaks at 521 and 539 nm) is strongly size-dependent at temperatures between 223 and 403 K. As the size of the spheres increases from 0.7 to 1.6 μm, the maximum sensitivity decreases from 36.8 × 10(-4) to 24.7 × 10(-4) K(-1). This effect is mainly attributed to the larger specific surface area of the smaller spheres where a relatively large number of Er(III) ions are located at the surface. This results in an increase in the efficiency of the (4)S3/2 → (2)H11/2 population process of the Er(III) ions due to stronger electron-phonon interactions with increasing T. Heating of the spheres by NIR light is also supposed to cause enhanced electron-phonon interactions in such particles.