The gallium chloro complex [GaCl{Fe(CO)2Cp}2] (Cp = η5-C5H5) was reacted with KP(SiMe3)2 under special conditions to yield the complexes [{CpFe(CO)}2{μ-(CO)}[μ-Ga{CpFe(CO)2}]] (1) and [{CpFe(CO)2}GaP(SiMe3)]4 (2). Furthermore, [[{CpFe(CO)2}ClGa](μ-PPh2)2FeCpCO] (4) was obtained by the reaction of [GaCl{Fe(CO)2Cp}2] with LiPPh2. Complexes 1, 2, and 4 have been characterized spectroscopically and by X-ray structure analysis. Complex 2 represents an ideal Ga4P4-heterocubane, the first Ga-containing example of this structural type with organometallic substituted group 13 elements. In the solid state compound 4 possesses an almost planar GaPFeP four-membered ring, a novel structural motif in mixed group 13/15 chemistry.