Multifunctional materials, which exhibit diverse physical properties, are candidates for the new generation of smart devices that realize many tasks simultaneously. Particular attention is given to single-phase multifunctional materials that offer the new physical effects induced by the coupling between introduced properties. Complexes of lanthanide(3+) ions are an attractive source of multifunctionality since they combine luminescent functionalities related to their f-f or d-f electronic transitions with magnetic anisotropy that originates from spin-orbit coupling and crystal-field effects. The resulting luminescent single-molecule magnets (SMMs) link the area of functional luminophores, applicable in light-emitting diodes or sensing, with the field of molecular magnets, applicable for high-density data storage, and offer additional advantages, e.g., fruitful magneto-optical correlations and the switching of emission by a magnetic field. It was recently shown that luminescent lanthanide SMMs can provide multifunctionality that is richly expanded towards their sensitivity to solvent exchange, temperature, or light, as well as the generation of electrical properties, such as super-ionic conductivity and ferroelectricity, or non-centrosymmetricity- and chirality-related effects, e.g., second-harmonic generation and circularly polarized luminescence. Here, we discuss the pioneering reports on multifunctional materials that use luminescent lanthanide SMMs, with the emphasis of our contribution relying on the functionalization of 4f metal complexes through their insertion into heterometallic d-f coordination compounds.