Ni2+/Yb3+/Er3+/Tm3+ codoped transparent glass-ceramics (GCs) containing both hexagonal -YF3 and spinel-like -Ga2O3 dual-phase nanoparticles (NCs) are synthesized by melt-quenching and subsequent heating procedures. Two techniques of transmission electron microscopy (TEM) nanoanalytics and optical spectroscopy are conjugated to understand the distribution of the rare-earth ions (REs) and transition metals (TMs) in the nanostructured GCs. It is found that the REs are located predominantly in -YF3, whereas the TMs in -Ga2O3 NCs. As a result, energy transfer (ET) between the REs and TMs is considerably suppressed due to the large spatial separation (> 3nm), but it is enhanced between the REs partitioned in the -YF3 NCs. This has important implications for intended and demanding photoluminescence functions. For example, an ultrabroadband near-infrared (NIR) emission in the wavelength region of 1000-2000nm covering the entire telecommunications window is observed for the first time. Meanwhile, intense upconversion (UC) emissions covering the 3 primary colors and locating in the first biological window can be also recorded under excitation by a single pump source at 980nm.