Three members of a new class of luminescent, neutral, and monomeric Be(II) complexes of aromatic N,O-chelate ligands, namely [Be(pbM)(2)] (1), [Be(pbX)(2)] (2), and [Be(pbt)(2)] (3) [Hpbm = 2-(2'-hydroxylphenyl)benzimidazole, Hpbx = 2-(2'-hydroxylphenyl)benzoxazole, and Hpbt = 2-(2'-hydroxylphenyl)benzothiazole], have been prepared and characterized by X-ray crystallography and photoluminescence studies. All the complexes are neutral, mononuclear molecules and display strong photoluminescence in the blue/green region, and thus, they may serve as candidates for electroluminescence materials. The electronic transitions in the photoluminescent process have also been investigated by means of time-dependent density functional theory (TDDFT) energy level and molecular-orbital analyses, showing that their absorption and luminescent properties are ligand-based and ligand-tunable.