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Polymorphism is often linked to the choice of processing solvents. Packing effects or the preference of one certain conformer as possible causes of this phenomenon are strongly dependent on solvents and especially on their polarity. Even in amorphous solids, the microstructure can be controlled by the choice of solvents. Polymorphs or amorphous solids featuring different packing densities can exhibit different properties in terms of stability or optical effects. The influence of these effects on a binuclear, strongly luminescent copper(I) complex was investigated. Many possible applications for luminescent, amorphous coordination compounds, such as organic light-emitting diodes, sensors, and organic lasers, rely on photophysical properties like quantum efficiency to be repeatable. The effect of processing solvents in this context is often underestimated, but very relevant for utilization in device manufacturing and should therefore be understood more deeply. In this work, theoretical derivations, DFT calculations, X-ray-diffraction, photoluminescence spectroscopy, and the time-dependent single-photon-counting-technique (TDSPC) were used to understand this phenomenon more deeply. The influence of five different solvents on Cu2I2(MePyrPHOS)3 was probed. This resulted in a modulation of the photoluminescence quantum yield ϕ between 0.5 and 0.9 in amorphous solid state. A new polymorph of the material with slightly reduced values for ϕ has been identified. The reduced efficiency could be correlated with a higher porosity and a reduced packing density. Dense packing reduces nonradiative decay by geometrical fixation and thus increases the quantum efficiency. The existence of similar effects on aluminum and iridium compounds has been confirmed by application of different processing solvents on Alq3 and Ir(ppy)3. These results show that a tuning of the efficiency of a emissive metal complexes by choosing a proper processing solvent is possible. If highly efficient materials for practical applications are desired, an evaluation of multiple solvents has to be considered.