Using confocal Raman and fluorescence spectroscopic imaging in 3-dimensions, we show direct evidence of inhomogeneous Nd(3+) distribution across grain boundaries (GBs) in Nd(3+):YAG laser ceramics. It is clearly shown that Nd(3+) segregation takes place at GBs leading to self-fluorescence quenching which affects a volume fraction as high as 20%. In addition, we show a clear trend of increasing spatial inhomogeneities in Nd(3+) concentration when the doping levels exceeds 3 at%, which is not detected by standard spectrometry techniques. These results could point the way to further improvements in what is already an impressive class of ceramic laser materials.