In this work, we have successfully fabricated hetero-structured nanofiber yarns (NFYs) with a conjugate electro-spinning technique, integrating a dual-functional capability of tunable color photoluminescence and tailored superparamagnetism. These hetero-structured NFYs are comprised of [Eu(BA)3phen + Tb(BA)3phen]/polyacrylonitrile (PAN) photoluminescent nanofibers (NFs) and Fe3O4/PAN superparamagnetic NFs, which allow for the effective isolation of dark-colored Fe3O4 nanoparticles (NPs) from rare earth complexes. This design leads to enhanced photoluminescent performance for the hetero-structured NFYs. Detailed investigations into the morphologies and performances of these NFYs were conducted using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), fluorescence spectrophotometry, and vibrating sample magnetometry (VSM). The emitting light color, ranging from red to yellow to green, can be tuned under a specific excitation wavelength (276 nm) of ultraviolet (UV) light by regulating the proportion of rare earth complexes. Furthermore, the superparamagnetism of the NFYs can be tailored by varying the amounts of Fe3O4 NPs. The designing philosophy and preparative technique can be utilized to manufacture other polyfunctional nanomaterials.