We report an unusual phenomenon in amplified spontaneous emission ͑ASE͒ from cyano-substituted oligo͑p-pheny lenevinylene͒ ͑CNDPASDB͒ single crystals, i.e., the ASE peak wavelength, exhibits varied dependence on the pumping wavelength ex. The former is basically kept a constant when ex Ͻ 505 nm, while a rapid redshift from 560 to 572 nm occurs when ex Ͼ 505 nm. The observation is different from stimulated Raman resonant scattering ͑SRRS͒ in two following aspects: the nonconstant Stokes shift and a much broader emission linewidth. A model describing competition between the stimulated emission and vibration relaxations has been proposed to interpret the underlying mechanism.