The tris[oligo1,4phenylenevinylene]carbinols 2a–fn=1–4 and the tris4styrylphenylmethanes 7a,bhave been prepared by Wittig–Horner 3+ 4a–f→ 2a–f and Siegristreactions 5+ 6a,b→ 7a,b. The Wittig–Horner reactions in these examples are accompanied by an autoxidation, whereas a reduction occurs in the Siegrist reactions. Compound 2a, the lowest member n= 1 of the series 2a–dwith terminal dialkylamino groups, generates first, on treatment with acids, the methylium dye 2′a, which absorbs far into the NIR region λmax= 1100 nm. The higher members 2b,cn= 2,3 of the carbinol series yield by acidic treatment only Nprotonated methylium dyes 2″′b,c. The different behavior is due to a decreasing donor–acceptor interaction with increasing D–A distance. The Nprotonated methylium salts 2″′a–cshow longwavelength absorptions in the region of the VisNIR border. Their values apporach, for increasing numbers nof repeat units, λ∞= 877 nm. The structures and possible push–pull effects of the salts 2′aand 2″′a–cwere studied by NMR and UVVisNIR spectroscopy and compared with the selected model compounds 2eand 7a. The results shed new light on previously published triphenylmethane dyes with extended conjugation. © WileyVCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009