Four new [Ni(Im)₆]²⁺-phosphorus compounds, namely, [Ni(Im)₆](PO₄)·ImH·4 H₂O (1), [Ni(Im)₆][Ni(AEDPH)(Im)₃]₂ (2) [Ni(Im)₆][Ni(AEDP)(Im)₃]·Im·3 H₂O (3), [Ni(Im)₆][Ni(Im)₃(APTPH)]·Im·ImH·8 H₂O (4), (AEDPH₄ = 1-aminoethylidenediphosphonic acid, APTPH₆ = 1-aminopropane-1,1,3-triphosphonic acid), are synthesized and characterized. These compounds illustrate various three-dimensional (3D) supramolecular structures. Compounds 1 and 2 both contain a two-dimensional (2D) packing arrangement of [Ni(Im)₆]²⁺ ions however they feature different sandwich-type structures: in 1, PO₄³⁻ ions and ImH⁺ ions are self-assembled to form a one-dimensional (1D) zigzag supramolecular chain; while a 2D pillared layer structure is generated by the interconnection of [Ni(AEDPH)(Im)₃]⁻ ions in 2. Compounds 3 and 4 both comprise a 1D packing arrangement of [Ni(Im)₆]²⁺ ions however they form dissimilar tessellate-type architectures: in 3, 1D double chain structure is constructed by [Ni(AEDPH)(Im)₃]²⁻ ions and Im molecules, whereas in 4, [Ni(Im)₃(APTPH)]³⁻ ions, Im molecules and ImH⁺ ions are integrated to generate a 3D supramolecular network with extended 1D channels. Moreover, compounds 1, 3 and 4 all contain diverse 1D water chain structures: C8 helix water chain in 1, C4 zigzag water chain in 3, and 1(1)8(1)C14 wavelike water chain in 4. The effects of phosphorus counterions on the structural types of the final products, as well as the hydrogen bond motifs, are also discussed in detail.