Solvent-dependent supramolecular isomers of a tripodal ligand incorporating two para-pyridylmethyl arms, N-naphthylmetyl-N,N-bis­(4-pyridylmethyl)­amine (L), are reported. A combination of L and copper­(II) hexafluoroacetylacetonate, Cu­(hfac)2, in methanol afforded a cyclic dimer complex [Cu2(L)2(hfac)4]·CH3OH (1). In chloroform/methanol, the same reaction furnished an infinite one-dimensional (1D) complex {[Cu2(L)2(hfac)4]·2CHCl3} n (2). When the cyclic dimer 1 was immersed in chloroform/ether, its transformation to the 1D coordination polymer 2 was observed in an single-crystal to single-crystal manner. In silver­(I) triflate complexations, three supramolecular isomers (3–5) were isolated. In chloroform/methanol, a multichannel-type three-dimensional (3D) coordination polymer {[Ag­(L)]­(CF3SO3)·0.5CHCl3} n (3) was isolated. In isomer 3, the Ag atom link L ligands alternately to form a helix, and these are linked by Ag–Ag contacts to generate an etb topology. In acetonitrile/methanol, a multichannel-type 3D coordination polymer {[Ag­(L)]­(CF3SO3)·CH3CN} n (4) was isolated. In isomer 4, six Ag atoms and six L ligands form an Ag6 L 6 hexagonal unit, and these are linked via Ag–Ag contacts, resulting in a pcu-h topology. In toluene/methanol/acetonitrile, a cross-linked ladder-type coordination polymer {[Ag4(L)4(CF3SO3)2]­(CF3SO3)2·3­(toluene)} n (5) was obtained. The isomer 5 is composed of two types of ladders crossed showing a new topology. Considering the formation of the (π–π)-(Ag–Ag)-(π–π) unit in 3–5, it is suggested that the anion–solvent interaction could be a major reason.