Here, we report a strategy for constructing {[Tb(BA) 3 phen + Eu(BA) 3 phen]/ PAN}//[PANI/PAN] (BA = benzoic acid, phen = phenanthroline, PANI = polyaniline, PAN = polyacrylonitrile) hetero-structured microyarns simultaneously endowed with the bi-functionality of tunable luminescence colors and electrical conductivity by using a conjugate electrospinning technique. The obtained hetero-structured microyarns are composed of [Tb(BA) 3phen + Eu(BA) 3 phen]/PAN luminescent nanofibers and PANI/PAN electrically conductive nanofibers, realizing efficient separation of dark-colored PANI from rare earth (RE) complexes, and thus the enhanced luminescent performance is obtained. Under 276-nm ultraviolet light excitation, the emitting light color of the hetero-structured microyarns can be adjusted in a broad range of green-yellow-red by changing the proportion of RE complexes. The electrical conductivity of the hetero-structured microyarns also can be modulated via tuning the percentages of PANI. These hetero-structured microyarns, by virtue of their luminescent properties and electrical performance, are expected to be applied in multifunctional applications.