The photo-stimulated luminescence spectroscopy (PSLS) technique provides the means to establish stress dependencies of the well-known R-line peak positions in polycrystalline alumina. The uniaxial compression tests presented in this paper, which determine the coefficients describing this piezospectroscopic (PS) behavior, tackle two previously unexplored areas. Firstly, the vibronic band peaks in the emission spectrum are introduced here, and the PS coefficients of several peaks within these bands are established. These results set the foundation for the exploitation of vibronic band peakshifts, along with the R-lines, in order to provide the non-symmetric components of the stress tensor and therefore the measurement of the complete stress state in polycrystalline alumina. Secondly, high-energy X-rays serve as an ex-situ stress measurement method upon which the optical fluorescence shifts are based, thereby advancing the accuracy of PS coefficient determination in a unique approach. The results of PSLS and synchrotron X-ray experiments are presented here and used in conjunction to reveal new information on the PS behavior of polycrystalline alumina.