The macromorphic properties of carbon nanotubes perform poorly because of their size limitations: nanosize in diameters and microsize in length. In this work, to realize these dual purposes, we first used an electrochemical method to tear the surface of multiwalled carbon nanotubes (MWCNTs) to anchor photonic Eu³⁺-complexes there. Through the polar reactive groups endowed by the tearing, the Eu³⁺-complexes coordinate at the defected structures, obtaining the Eu³⁺-complex-anchored, unzipped, multiwalled carbon nanotubes (E-uMWCNTs). The controllable surface-breaking retains the MWCNTs’ original, excellent mechanical properties. Then, to obtain the macromorphic structure with infinitely long fibers, a wet-spinning process was applied via the binding of a small quantity of polyvinyl alcohol (PVA). Thus, the wet-spun fibers with high contents of E-uMWCNTs (E-uMWCNT-Fs) were produced, in which the E-uMWCNTs took 33.3 wt%, a high ratio in E-uMWCNT-Fs. On the other hand, due to the reinforcing effect of E-uMWCNTs, the highest tensile strength can reach 228.2 MPa for E-uMWCNT-Fs. Meanwhile, the E-uMWCNT-Fs show high-efficiency photoluminescence and excellent media resistance performance due to the embedding effect of PVA on the E-uMWCNTs. Therefore, E-uMWCNT-Fs can exhibit excellent luminescence properties in aqueous solutions at pH 4~12 and in some high-concentration metal-ion solutions. Those distinguished performances promise outstanding innovations of this work.