Reactions between the five-fold symmetric building block [Cp*Fe(η5-P5)] (A) and Ag(I) salts containing bulky weakly coordinating anions [TEF] and [FAL] ([TEF] = [Al{OC(CF3)3}4]–, [FAl] = [FAl{OC6F10(C6F5)}3]–) are presented. While, in the presence of Ag[TEF], A leads to the formation of a hitherto condensed 1D coordination polymer [{Ag( η 2 : η 1 -A)2}]n[TEF]n (1), a new finite tetranuclear Ag(I) complex [{Ag4( η 1 -A)2( η 2 : η 1 -A)4( η 1 : η 1 -A)2}][FAL]4 (3) was obtained with an Ag(I) salt bearing the weakly coordinating anion [FAl] increased in size . Various coordination modes ( η2: η1; η1: η1 and η1) of A were observed in the solid-state structure of 3, reflecting the adaptive coordination behavior of A towards Ag(I) ions. Structural modifications of the 1D polymer (1) can be controlled by the addition of a trace amount of MeCN yielding the unwound heteroleptic 1D polymer [{Ag(MeCN)2}3( η 1 : η 1 : η 1 -A)2]n[TEF]3n (2) . Moreover, in the presence of MeCN, the finite oligomeric compound 3 can also be converted into a new heteroleptic 1D polymer [{Ag(MeCN)}4( η 1 : η 1 -A)5( η 2 : η 1 -A)2]n[FAL]4n (4).