A new heteroleptic ID Cu-I-Re-IV coordination polymer of the formula {(CuReCl4)-Re-I-Cl-IV(mu-Cl)(mu- pyz)[(ReCl4)-Cl-IV(mu-bpym)]}(n)center dot nMeNO(2) (1; pyz = pyrazine, bpym = 2,2'-bipyrimidine) has been prepared through the Cu-I-mediated self-assembly of two different Rely metal-loligands; namely, [ReCl5(pyz)](-) and [ReCl4(bpym)]. 1 consists of chiral branched-chains with an overall tack-type architecture displaying photoemission and magnetic ordering. These results constitute a first step toward making new multifunctional magnetic materials based on mixed 3d-5d molecular systems.