The new, sterically encumbered phenanthroline ligands 1a,b, both characterized by the presence of bulky aryl substituents (3,5-di-tert-butyl-4-methoxyphenyl, 2,4,6-trimethylphenyl) in the 2,9-position, were prepared along with their homoleptic [Cu(1a,b)(2)](+) and heteroleptic complexes [Cu(1a,b)(phen)](+) (phen = parent 1,10-phenanthroline). Due to the pronounced steric shielding, particularly effective in ligand la, the formation of the homoleptic complex [Cu(1a)2]+ becomes very slow (5 days). Once formed, the homoleptic complexes [Cu(1a,b)2]+ do not exchange ligands even with phen added in excess because they are kinetically locked due to the large tert-butylphenyl substituents at the phenanthroline unit. The electronic absorption spectra of the homoleptic complexes [Cu(1a)(2)](+) and [Cu(1b)(2)](+) evidence a strongly different ground state geometry of the two compounds, the former being substantially more distorted. This trend is also observed in the excited-state geometry, as derived by emission spectra and lifetimes in CH2Cl2 solution. The less distorted [Cu(1b)(2)](+), compared to [Cu(1a)(2)](+), is characterized by a 15- and over 100-fold stronger emission at 298 and 77 K, respectively. Noticeably, the excited-state lifetime of [Cu(1a)(2)](+) in solution is unaffected by the presence of molecular oxygen and only slightly shortened in nucleophilic solvents. This unusual behavior supports the idea of a complex characterized by a "locked" coordination environment.