In this paper, three pure inorganic eight-connected self-catenated networks based on the Silverton-type polyoxometalate [CeMo 12 O 42 ] 8− with lanthanide, transition metal and alkali metal cations as linkers: [Li(H 2 O) 4 ] 2 Co(H 2 O) 4 Ce(H 2 O) 3 [CeMo 12 O 42 ]·3H 2 O (1), H 0.5 [Li(H 2 O) 4 ] 2.5 [Ni(H 2 O) 4 ] 0.5 Ce(H 2 O) 3 [CeMo 12 O 42 ]·3H 2 O (2) and H[Li(H 2 O) 4 ] 3 Ce(H 2 O) 3 [CeMo 12 O 42 ]·3H 2 O (3) have been successfully synthesized and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, X-ray photoelectron spectroscopy, electrochemical analyses and single crystal X-ray diffraction. The single crystal X-ray diffraction analyses reveal that compounds 1–3 are isostructural. The [Ce IV Mo 12 O 42 ] 8− polyoxoanions are connected by Ce 4+ to form the infinite 1D chains. And then the parallel stacking chains linked by transition metal cations and lithium ions construct to an eight-connected self-catenated 4 24 56 3 topology framework.