Five novel 2,3-naphtho crown ether group 10 metal bis(dithiolate) complexes, [Na(N15C5)2]2[Pd(mnt)2] (1), [Na(N15C5)]2[Pd(i-mnt)2] (2) and [K(N18C6)]2[M(i-mnt)2] (35) (where mnt = 1,2-dicyanoethylene-1,2-dithiolate, i-mnt = 1,1-dicyanoethylene-2,2-dithiolate and M = Ni, Pd, Pt for complexes 3–5, respectively), have been synthesized and characterized by elemental analysis, FT-IR, UV–Visible spectra and single crystal X-ray diffraction. X-ray diffraction analyses reveal that complexes 1 and 2 have different structural features while complexes 3–5 are structurally isomorphous. Complex 1 consists of two [Na(N15C5)2]+ sandwich complex cations and one [Pd(mnt)2]2− anion, affording a zero-dimensional structure. For 2, the [Na(N15C5)]+ mono-capped complex cations act as the bridges linking the [Pd(i-mnt)2]2− anions into a 1D infinite chain through Na–N interactions and SȮFC and SȮFπ interactions are observed in the resulting chain. Complexes 3–5 all consist of two [K(N18C6)]+ complex cations and one [M(i-mnt)2]2− (M = Ni, Pd or Pt) anion and the complex molecules are linked into␣1D␣chains by the bridging K–O(ether) interactions between the adjacent [K(N18C6)]+ units. What’s novel is that the resulting chains are assembled into novel 2D networks through interchain π–π stacking interactions between the neighboring naphthylene moieties of N18C6. The stack model of naphthylene group in complexes 3–5 is discussed.