The steric strain around copper(I) in typical [Cu(NN)] complexes, where NN is a diimine ligand substituted in α-positions of the nitrogen atoms by R, is known to strongly impact the excited-state properties. Generally speaking, the larger the R, the longer the emission lifetime and the higher the quantum yield. However, the stability of the coordination scaffold can be at stake if the steric strain imposed by R is too large. In this work, we explore a way of fine-tuning the steric strain around Cu(I) to reach a balance between high emission quantum yield and stability in a highly bulky copper(I) complex. Taking stable [Cu(dipp)] and unstable [Cu(dtbp)] (where dipp and dtbp are, respectively, 2,9-diisopropyl-1,10-phenanthroline and 2,9-di--butyl-1,10-phenanthroline) as the boundary of two least and most sterically strained structures, we designed and characterized the nonsymmetrical ligand 2-isopropyl-9--butyl-1,10-phenanthroline (L1) and corresponding complex [Cu(L1)] (Cu1). The key experimental findings are that Cu1 exhibits a rigid tetrahedral geometry in the ground state, close to that of [Cu(dtbp)] and with an intermediate stability between that of [Cu(dipp)] and [Cu(dtbp)]. Conversely, the nonsymmetrical nature of ligand L1 leads to a shorter emission lifetime and smaller quantum yield than those of either [Cu(dipp)] or [Cu(dtbp)]. This peculiar behavior is rationalized through the in depth analysis of the ultrafast dynamics of the excited state measured with optical transient absorption spectroscopy and theoretical calculations performed on the ground and excited state of Cu1. Our main findings are that the obtained complex is significantly more stable than [Cu(dtbp)] despite the sterically strained coordination sphere. The nonsymmetrical nature of the ligand translates into a strongly distorted structure in the excited state. The distortion can be described as a rocking motion of one ligand, entailing the premature extinction of the excited state via several deactivation channels.