Decomposition of rare-earth tris(N, N'-diisopropyl-2-methylamidinato)metal(III) complexes [RE(MeC(N(iPr)₂))₃] (RE(amd)₃; RE = Pr(III), Gd(III), Er(III)) and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)europium(III) (Eu(dpm)₃) induced by microwave heating in the ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF₄]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIm][NTf₂]) and in propylene carbonate (PC) yield oxide-free rare-earth metal nanoparticles (RE-NPs) in [BMIm][NTf₂] and PC for RE = Pr, Gd and Er or rare-earth metal-fluoride nanoparticles (REF₃-NPs) in the fluoridedonating IL [BMIm][BF₄] for RE = Pr, Eu, Gd and Er. The crystalline phases and the absence of significant oxide impurities in RE-NPs and REF₃-NPs were verified by powder X-ray diffraction (PXRD), selected area electron diffraction (SAED) and highresolution X-ray photoelectron spectroscopy (XPS). The size distributions of the nanoparticles were determined by transmission electron microscopy (TEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) to an average diameter of (11 ± 6) to (38 ± 17) nm for the REF₃-NPs from [BMIm][BF₄]. The RE-NPs from [BMIm][NTf₂] or PC showed diameters of (1.5 ± 0.5) to (5 ± 1) nm. The characterization was completed by energy-dispersive X-ray spectroscopy (EDX).