In order to enrich the chemistry of the Fe/Te cluster compounds related to the active site of the [FeFe]-hydrogenase, the reactions of compound Fe₂(μ-TeAr)₂(CO)₆ with tertiary phosphines were described. Three types of novel phosphine substituted Fe/Te model compounds were successfully prepared. That is, the treatment of Fe₂(μ-TeAr)₂(CO)₆ (Ar = C₆H₅A, C₆H₄-F-4 B) with 2 equivalents of PPh₃ under UV conditions produced dinuclear compounds Fe₂(μ-TeC₆H₅)₂(CO)₄(PPh₃)₂ (1) and Fe₂(μ-TeC₆H₄-F-4)₂(CO)₄(PPh₃)₂ (2) in moderate yields together with unusual tetranuclear compounds Fe₄(μ-TeC₆H₅)₆(CO)₆(PPh₃)₂ (3) and Fe₄(μ-TeC₆H₄-4-F)₆(CO)₆(PPh₃)₂ (4). The syn- and anti-isomers of 1 and 2 were isolated in the solid state using the TLC method. Furthermore, the reaction of Fe₂(μ-TeAr)₂(CO)₆ and 4 equivalents of PMe₃ gave new types of mononuclear PMe₃-disubstituted compounds Fe(TeC₆H₅)₂(CO)₂(PMe₃)₂ (5) and Fe(TeC₆H₄-4-F)₂(CO)₂(PMe₃)₂ (6) which could mimic Fe_d of the [FeFe]-hydrogenase. All the new compounds were fully characterized by elemental analysis, IR, NMR spectroscopy, UV-Visible absorption and particularly some of them by X-ray crystallography. The electrochemical properties of 1, 2, 5 and 6 were also investigated, demonstrating that these compounds can be considered as electrochemical catalysts for the hydrogen evolution reaction. According to the electrochemical behavior of 5 and 6, a CEECC mechanism was proposed for the catalytic process.