Luminescent [Cu2I2(pyrpy)(2)(PR3)(2)] complexes (pyrpy = 4-pyrrolidinopyridine; PR3 = triphenylphosphine (1), tri-m-tolylphosphine (2), tri-p-tolylphosphine (3)) were prepared by solution reactions and a rarely reported solvent-free thermal method. X-ray structure analyses reveal that complexes composed of dinuclear {Cu2I2} cores surrounded by two PR3 and two pyrpy ligands were formed. Although the melting point of pyrpy is the lowest among the organic units used in this study, the temperature required to form the luminescent dinuclear complex, prepared by the thermal synthesis method, depended strongly on the PR3 moiety. Two of the three complexes (1 and 3) were successfully prepared by the solvent free thermal method. Complexes 1-3 exhibited blue emissions at around 450 nm with moderately high quantum yields (Phi) of 0.24, 0.31, and 0.51, respectively. Emission-lifetime measurements and time-dependent density functional theory (TD-DFT) calculations suggest thermally activated delayed fluorescence (TADF) in each complex. This solvent-free thermal synthesis of TADF materials represents a promising method for the preparation of luminescent layers directly onto substrates of thin-layer electronic devices, such as organic light-emitting diodes.