Organometallic hydrazines of general formula [(η⁵-Cp)Fe(η⁶-p-RC₆H₄NHNH₂)]⁺PF₆^- (Cp=C₅H₅; R=H, (1)⁺PF₆^-; Me, (2)⁺PF₆^-; MeO, (3)⁺PF₆^-; Cl, (4)⁺PF₆^-) react with equimolar quantities of (E)-4-(2-ferrocenylvinyl)-benzaldehyde, (E)-[(η⁵-Cp)Fe(η⁵-C₅H₄)–CH=CH–C₆H₄CHO], to afford stereoselectively, the new homodimetallic hydrazones formulated as (E)-[(η⁵-Cp)Fe(η⁶-p-RC₆H₄)–NHN=CH–C₆H₄–CH=CH–(η⁵-C₅H₄)Fe(η⁵-Cp)]⁺PF₆^- (R=H, (5)⁺PF₆^-; Me, (6)⁺PF₆^-; MeO, (7)⁺PF₆^-; Cl, (8)⁺PF₆^-). These compounds were fully characterized by elemental analysis and spectroscopic techniques (¹H- and ¹³C-NMR, IR and UV-vis) and, in the case of complex (6)⁺PF₆^-, by single crystal X-ray diffraction methods. The rotations of the ferrocenyl unit by 37.2° out of the –NHN=CH–C₆H₄–CH=CH– spacer and coordinated phenyl ring planes, may generate an unfavorable structure to allow π-electron delocalization along the entire hydrazonato backbone between the two metals separated through bonds by more than 1.8 nm, as confirmed by the electrochemical data.