A series of 4,4′-disubstituted organic−organometallic stilbenes, i.e., the 4′-substituted stilbenoid-NCN-pincer platinum(II) complexes [PtCl(NCN-R-4)] (NCN-R-4 = [C6H2(CH2NMe2)2-2,6-R-4]− in which R = C2H2C6H4-R′-4′ with R′ = NPh2, NMe2, OMe, SiMe3 H, I, CN, NO2) (1−8), were studied for their electronic, electrochemical, and NLO properties. Complex 7 was also chemically oxidized using Cu(II)Cl2, yielding the [Pt(IV)Cl3(NCN(C2H2C6H4-CN-4′)-4)] complex 11. In contrast to 1 and 7, 11 did not show luminescent properties in solution at room temperature. In the solid state (X-ray crystallography) 11 has an overall bent structure, with the pincer moiety and the cyano group beneath the plane of the central double bond. Stilbenoid pincer complex 1 (R′ = NPh2) was also studied with UV/vis spectroscopy in a series of different solvents. The compound shows an intense low-energy transition band, appearing at a lower energy (λmax = 374–379 nm) than 2 (R′ = NMe2), which contains a stronger donor group. The UV/vis absorp...