7,7,8-Tris(alkoxycarbonyl)-8-cyanoquinodimethanes (1) with ethoxy (1a), methoxy (1b), isopropoxy (1c), butoxy (1d), and tert-butoxy (1e) alkoxy groups were successfully prepared as pure, isolable yellow crystals. Compounds 1a and 1e formed charge-transfer complexes not only with styrene (St) but also with 7,7,8,8-tetracyanoquinodimethane (TCNQ), indicating that 1a and 1e exhibited an amphoteric polar character in the charge-transfer complex formation. When 1a-e were dissolved in basic polar aprotic solvents such as acetone, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, and dimethyl sulfoxide, 1a-d, but not 1e, spontaneously polymerized to give polymers. Compounds 1a-e were homopolymerizable with 2,2’-azobis(isobutyronitrile) (AIBN) and butyllithium but not with boron trifluoride etherate. Compound le had a very poor polymerizability compared with 1a-d, probably due to the steric hindrance of the tert-butyl group. Homopolymerizable compound la copolymerized with St in the presence of AIBN to obtain the monomer reactivity ratios r(1a) = 1.62 +/- 0.28 and r(St) = 0.005 +/- 0.01 at 60 degrees C and Q and e values of Q = 30.5 and e = +1.40, indicating that 1a is highly conjugative (highly reactive) and electron-accepting and copolymerized with acceptor monomer TCNQ in a perfectly alternating fashion. Poorly homopolymerizable compound 1e also copolymerized not only with donor monomer St but also with acceptor monomer TCNB in a perfectly alternating fashion, indicative of the amphoteric polymerization behavior of 1e. Compounds 1a and 1e were found to be isolable 1,4-quinodimethane monomers which exhibited amphoteric behavior in the charge-transfer complex formation as well as in the alternating copolymerization.