The reaction of 2‐aminonicotinaldehyde with 2‐ or 4‐methoxyacetophenone in basic media leads to the new ligands 2‐(4‐methoxyphenyl)‐1,8‐naphthyridine and 2‐(2‐methoxyphenyl)‐1,8‐naphthyridine, respectively, in high yield. The reaction of these naphthyridine derivatives with [RuCl2(CO)2]n leads to the respective complexes cis‐dicarbonyldichloridobis[2‐(4‐methoxyphenyl)‐1,8‐naphthyridine‐κN8]ruthenium(II) and cis‐dicarbonyldichloridobis[2‐(2‐methoxyphenyl)‐1,8‐naphthyridine‐κN8]ruthenium(II), both [RuCl2(C15H12N2O)2(CO)2], in good yield. Both ruthenium(II) complexes display a slightly distorted octahedron with two cis carbonyl, two cis chloride and two cis naphthyridine ligands, the latter coordinated in a monodentate fashion through the N atom in the 8‐position. Both complexes exhibit a moderate catalytic activity in the hydrogen‐transfer reaction from propan‐2‐ol to acetophenone in the presence of a base, with 100% selectivity.