Luminescence from a square planar [Pd(SCN)(4)](2-) complex shows very large increases in intensity and lifetime from ambient pressures up to 27 kbar. The band maximum shows a blue-shift of approximately 29 cm(-1)/kbar. These spectroscopic observations can be rationalized qualitatively by considering multiple effects, and they underline the strong interrelation between molecular structure, energies, and geometries of excited electronic states, and optical properties.