Incorporation of Eu complexes into various organic or inorganic matrixes is one of the acceptable strategies to obtain displaying materials having practical applications. In this work, we report a convenient approach to preparing high luminescent organic-inorganic hybrid materials and films from the europium-titanium oxo-clusters (EuTOCs) having photoactive antenna ligands. Three Eu2Ti4 oxo-clusters were synthesized and crystallographically characterized. They are the first reported lanthanide-TOCs coordinated with 1,10-phenanthroline (phen) and 2,2'-bipyridine (bpy) as photoactive ligands, Eu2Ti4O6(phen)(2)(pa)(10) (1) (pa = propionate), Eu2Ti4O6(bpy)(2)(pa)(10) (2), and Eu2Ti4O6(phen)(2)(MA)(10) (3) (MA = methacrylate). Benefitting from the photoactive antenna ligands and the rigid cluster structures, these clusters showed bright red luminescence with quantum yield in the range of 60-80% and long lifetime up to 3.0 ms. Unlike those physically mixed polymeric materials, the MA coordinated compound 3 can be self-polymerized to form a brilliant luminescent film. The film coated slide was used to develop a fluorescence sensor for biomolecule ascorbic acid (AA). The low detection limit and reusable properties suggest great potential for such EuTOC films in real applications.