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Details of the structure–property correlation in organic light-emitting diodes (LEDs) are reported for the oligophenylenevinylene (OPV) system. The electroluminescence (EL) characteristics of 6-OPV (n equals; 2 in the Figure) and 10-OPV (n equals; 4 in the Figure) are compared and an explanation is proposed for the shift and broadening of the EL spectra under different driving voltages.