Triads with extended conjugated p-electronic systems between polyhedral cage molecules possess promising electronic properties. In contrast to the known fullerenebridgefullerene triads, fewer synthetic procedures are known for the related homoatomic deltahedral cage molecules of the heavier homologues of carbon. The synthesis of the organo-Zintl triads [RGe9CH=CH=CH=CHGe9R](4) with R = -CH=CH2 (R-1), -C(CH3)-CH=CH-N(CH2)(2)NH2 ((2Z,4E)-7-amino-5-azahepta-2,4-dien-2-yl) (R-2) is reported, in which the deltahedral Ge-9 cages carry an additional functional group, allowing for further connections. Both anionic cage entities bear a butadiene-1,4-diyl bridge which is formed by reacting the Zintl ion [Ge-9](4) with 1,4-bis(trimethylsilyl)butadiyne in ethylenediamine. The organic tethers can be attached by nucleophilic attack of the Ge-9 clusters at the bis(trimethylsilyl)acetylene and (3Z/3E)-7-amino-1-(trimethylsilyl)-5-azahepta-3-en-1-yne, respectively, in ethylenediamine, and the products cis/trans-[R1Ge9CH=CH=CH=CHGe9R1](4) and cis/cis-[R2Ge9CH=CH=CH=CHGe9R2](4) have been isolated as [A(2,2,2-crypt)]+ salts with A = K, Rb, respectively. Crystals containing the novel anions [RGe9CH=CH=CH=CHGe9R](4) have been structurally characterized by X-ray diffraction methods, and the compounds have been investigated by 1H and C-13 NMR as well as by Raman spectroscopy. The cis/cis configurational isomer of [R1Ge9CH=CH=CH=CHGe9R1](4) was characterized by means of NMR spectroscopy. Via in situ NMR measurements, we shed some light on the formation of the Zintl triads [RGe9CH=CH-CH=CHGe9R](4) bearing supplemental organic tethers.