Flexible peculiarly structured [(Fe3O4/PVP)@(Tb(BA)(3)phen/PVP)]//[PANI/PVP] (PVP=polyvinylpyrrolidone, BA=benzoic acid, phen=1,10-phenanthroline, and PANI=polyaniline) Janus nanofibers synchronously endowed with tuned and enhanced luminescent-magnetic-electrical trifunctionality have been prepared by electrospinning technology by using a homemade coaxis//monoaxis spinneret. It is satisfactorily found that the luminescent intensity of the peculiarly structured Janus nanofibers is higher than those of the counterpart conventional [nanofiber]//[nanofiber] Janus nanofibers and composite nanofibers owing to its peculiar nanostructure. Compared with the counterpart conventional Janus nanofibers of two independent partitions, the coaxial nanocable is used as one side of the peculiarly structured Janus nanofiber instead of nanofiber, and three independent partitions are successfully realized in the peculiarly structured Janus nanofiber, thus the interferences among various functions are further reduced, leading to the fact that excellent multifunctionalities can be obtained. The Janus nanofibers possess excellent green luminescence, superparamagnetism, and electric conductivity, and further, these performances can be, respectively, tunable by modulating the Tb(BA)(3)phen, Fe3O4, and PANI contents. The design philosophy and construction technique for the peculiarly structured Janus nanofibers provide guidance for fabricating other multifunctional Janus nanofibers with various performances.