1-[3,5-Bis (N,N-dimethylamino)phenoxyl-omega-(2,4,6-tricyanophenylthio)alkanes (1a-c), where an electron-accepting 2,4,6-tricyanophenylthio group and an electron-donating 3,5-bis(N,N-dimethylamino)phenoxy one are linked with a spacer such as ethylene, trimethylene, and tetramethylene, were prepared in order to examine an effect of the spacer chain length on intramolecular charge-transfer interaction between the 2,4,6-tricyanophenylthio and 3,5-bis(N,N-dimethylamino)phenoxy groups. From the UV-vis spectra measurements of 1a-c, 1-[3,5-bis(N,N-dimethylamino)phenoxy]-3-(2,4,6-tricyanophenylthio)propane (1b) carrying the trimethylene chain as a spacer was found to have the strongest intramolecular charge-transfer interaction. A new methacrylate-type monomer carrying the 1b unit as a side chain, 1-(2,4,6-tricyanophenylthio)-3-[3,5-bis( N,N-dimethylamino)phenoxy-2-propyl methacrylate (2), was prepared successfully in 9.2% total yield in seven steps. The monomer 2 homopolymerized in benzene, tetrahydrofuran, acetone, and dimethyl sulfoxide in the presence of 2,2’-azobis(isobutyronitrile) at 60 degrees C to give polymers [poly(2)] with molecular weights of 6,000 to 98,000. An intramolecular charge-transfer interaction in the poly(2) was found to be larger than that in the monomer 2 and to increase with an increase in the degree of polymerization of the poly(2), suggesting that there is an existence of polymer effect other than the polymer effect due to the high local concentration of the donor-acceptor pair.