A novel one-dimensional (1D) heterometallic chain, {[Rh-2(dfpma)(2)-(MeCN)(4)](2)[Ag(MeCN)(4)]}[PF6](5) (1), is afforded from the in situ reaction of [ClRh(cod)](2) with [Ag(MeCN)(4)][PF6] and dfpma (dfpma = bis(difluorophosphine)methylamine). Dichroic crystals, which are obtained from MeCN/Et2O solutions, crystallize in the monaclinic space group C2/m with a = 13.570(5) Angstrom, b = 20.895(9) Angstrom, c = 13.810(6) Angstrom, beta = 104.904(7)degrees, V = 3784(3) Angstrom(3), Z = 4. X-ray diffraction studies reveal an asymmetric unit comprising two Rh-2(l) dimers and a square planar Ag-l cation; this subunit propagates to form a 1D heterometallic chain. Compound 1 displays novel spectroscopic properties in the solid state, including temperature-dependent luminescence.