Three novel coordination polymers have been synthesized by reacting cis- and trans-alkyne-appended cydodiphosphazanes with CuX (X = Br, I) salts. The reaction of cis-[(PhC CP)(2)(mu-(NBu)-Bu-t)(2)] (1) with CuBr in a 1:3 molar ratio gave a 3D coordination polymer, [{Cu-4(mu(3)-Br)(4)}{(cis-(PhC CP)(2)(mu-(NBu)-Bu-t)(2))-Cu-4(mu(2)-Br)(4)(cis-(PhC CP)(2)(mu-(NBu)-Bu-t)}(2))(4)](n) (3), having diamondoid topology with an unprecedented copper alkyne coordination, whereas the reaction of 1 with CuI in a 1:4 molar ratio afforded a ID polymeric complex, [{Cu-4(mu(3)-I)(4)}(NCCH3)(2){cis-(PhC CP)(2)(mu-(NBu)-Bu-t)(2)}](n)(4). In contrast, the reaction of trans-[(PhC CP)(2)(mu-(NBu)-Bu-t)(2)] (2) with CuI was found to be independent of stoichiometry and afforded a 3D coordination polymer, [{Cu-4(mu(3)-I)(4)4}{trans-(PhC CP)(2)(mu-(NBu)-Bu-t)(2)}(2)](n) (5), exclusively.