Rare-earth-doped upconversion (UC) materials are ideal candidates for solar photovoltaic conversion and NIR response devices due to their unique spectral conversion properties. However, their low efficiency remains a tremendous challenge for practical applications. Here, we constructed an efficient NIR light-responsive device by coating a Si-photoresistor with a transparent gel consisting of UC powders and an organic polymer matrix. We show that reasonable introduction of alkali metal ions (Na+, K+, and Cs+) into the lattice of UC crystals results in the improvement of photoelectricity conversion efficiency, due to the high crystallinity and surface reconstruction caused by alkali metal ion doping.