Novel poly(dimethylsilyleneethynylenephenylene) [5] and poly(dimethyl (or diphenyl) silylenephenyleneethynylenephenylene)s [6's] without diyne defects were synthesized by using the Pd/Cu-catalyzed AB-type coupling reaction. 6's showed small but clear pi-to-sigma charge-transfer absorption bands at longer wavelengths (>340 nm) than those of pi-pi* absorption bands (<320 nm), whereas the charge-transfer absorption band was not found in 5. When 6's were excited at the absorption wavelengths, two type of emission were observed: One is the vibronically structured emission with a maximum around 325 nm due to the locally excited pi* state, and the other is the intramolecular charge-transfer emission having a broad and structureless band (emission lambda(max) ca. 370 nm) with a large Stokes shift. On the other hand, when excited at the charge-transfer absorption wavelengths, 6's exhibited only the intramolecular charge-transfer emission with a maximum above 390 run. This suggests that the indigo blue light emission of 6's is due to the charge-transfer phenomenon and not to the locally excited pi* state. The charge-transfer character of 6's was clearly verified by the shift of emission in polar solvents.