We present a spectroscopic study of the green fluorescence resulting from pump excited-state absorption in Er-doped silica fibers excited in the 800-nm range. The absorption and emission bands are selectively attributed to the (4)S(3/2) and (2)H(11/2) levels. The fluorescence response at two excitation wavelengths, the temperature behavior, and lifetime measurements demonstrate a fast thermalization between the (4)S(3/2) and (2)H(11/2) levels. This explains an important part of the (2)H(11/2) emission and the increase of the fluorescence intensity at high temperature.