Lanthanide luminescent complexes are active and thriving in various research fields due to their unique optical properties, while optical materials across a wide spectral range and with multiple functions in one were rarely reported. In this work, a new class of Ln³⁺/Al³⁺ metallacrowns (MCs) were constructed with excellent luminescence properties in both the visible and near-infrared regions, and the elaborate luminescence modulation can be achieved by doping with different Ln³⁺ ions. Strikingly, the powder of LnMC was developed as a luminescent nanomaterial for the detection of latent fingerprints (LFPs), and even the third level details of fingerprints can be clearly recognized, which provides a reference for the identification of fingerprints in the field of criminal investigation. More importantly, TbMC and Tb_0.1Sm_0.9MC can be successfully used as luminescent thermometers with sensitivities of 2.51% °C⁻¹ and 2.33% °C⁻¹, respectively, higher than most reported values. Meanwhile, TbMC was developed as a luminescent probe for Fe³⁺ and 2,6-pyridinedicarboxylic acid (DPA) with low limits of detection (LOD) of 0.51 μM and 4.26 μM, respectively, representing the first example of MC with luminescence sensing. Also of note is that SmMC, Tb_0.1Sm_0.9MC and TbMC can be functionalized as luminescent inks and films due to their clear recognizable colours in the visible range, suggesting a new strategy for high-level anti-counterfeiting. In short, the LnMC luminescent material has wide application prospects in many fields, especially rare for multifunctional applications of small-molecule complexes with non-metal–organic frameworks.