Functional crystalline materials based on bimetallic cyanido-bridged {[Dy-III(4-Mephen)(dmf)(4)]-[M-V(CN)(8)]}center dot 0.5H(2)O (M = Re, 1; Mo, 2; W, 3; 4-Mephen = 4-methyl-1,10-phenanthroline) helices have been prepared. 1 is the first heterometallic coordination polymer incorporating an unexplored [Re-V(CN)(8)](3-) ion. Implementation of the Re-V-based diamagnetic analogue of broadly investigated paramagnetic [Mo-V(CN)(8)](3-) and [W-V(CN)(8)](3-) ions into the d-f coordination framework results in yellow photoluminescence originating from F-4(9/2) -> H-6(j) f-f electronic transitions of Dy-III sensitized by 4-Mephen, and field-induced slow magnetic relaxation related to the single-ion anisotropy of the dysprosium(III) complexes. We prove that [Re-V(CN)(8)](3-) can work as a noninnocent metalloligand in the preparation of emissive 4f-metal-based single-molecule magnets.