Described herein is the synthesis and photophysics of two tetranuclear copper complexes, {[3,5-(Pri)2,4-(Br)Pz]Cu}4 and {[3-(CF3),5-(But)Pz]Cu}4 tailor-designed by manipulating the pyrazolyl ring substituents. Unlike their trinuclear analogues, the luminescence of the tetranuclear species is molecular (not supramolecular) in nature with extremely high solid-state quantum yields of ∼80% at room temperature.