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• Five new alkali metal complexes (1 – 5) with nirogen and oxygen donor ligands have been synthsized and charcterized by infrared and UV–vis spectroscopy, elemental analysis, 1H NMR, and single-crystal X-ray diffraction analysis. • The complexes displayed excellent activities against oral and lung cancer cells with the least toxicity toward normal cells. In this report, we present five new alkali metal complexes (1 – 5) that displayed excellent anticancer and antibacterial activities in solutions. 1,10-phenanthroline (phen), salicylic acid (sa) benzoic acid (ba), and p-aminobenzoic acid (paba) ligands were employed in complexation reactions. The complexes were characterized by a variety of analytical techniques including infrared and UV–vis spectroscopy, elemental analysis, 1H NMR, 13C NMR, and single-crystal X-ray diffraction analysis. We described the structures of three mononuclear lithium complexes [Li(phen) 2 (sal)] (1), [Li(phen) 2 (ba)] (2), {[Li(phen)(H 2 O) 3 ].(paba)} (3), a mononuclear sodium complex [Na(phen)(paba)(H 2 O)] (4) and an unsual tetranuclear cesium complex [Cs 4 (phen) 4 (paba) 4 (H 2 O) 2 ] (5). The complexes in solution displayed excellent activities against oral and lung cancer cells with the least toxicity toward normal cells when compared to the standard drug 5-fluorouracil and cisplatin. [Display omitted] [ABSTRACT FROM AUTHOR]