Integrating luminescent nanomaterials into hydrogels provides unique optical properties and improves their mechanical features for various applications. It is challenging but highly desirable to develop a versatile luminescent nanocomposite hydrogel system with tunable structures and properties to expand the potential uses of luminescent materials. Here, multiple amine-functionalized lanthanide-containing hydroxyapatites are synthesized as tailored nanomaterial cross-linkers to interact with polydextran aldehyde through imine bonds. The microstructure, gelation time, luminescence, rheological behavior, mechanical properties, thermal stability, degradation, and swelling capability of the luminescent lanthanide-containing nanocomposite hydrogels are systematically investigated. This study reveals that the strong binding affinity between surface metal ions and capping ligands of the nanomaterial cross-linkers contributes to the densest network and the highest mechanical properties of the nanocomposite hydrogels. In addition, these nanocomposite hydrogels possess dynamic features of self-healing, shear-thinning, and injectability, improving their suitability for advanced applications. The luminescent lanthanide-containing nanocomposite lyophilized hydrogels are also demonstrated in the differentiation of volatile organic compounds. Taken together, the adjustable microstructures and characteristics of this lanthanide-containing nanocomposite hydrogel system highlight its potential for offering guidance in producing diverse luminescent materials with definable performances across various fields.