Anion–cation radical formation in solid films of M3EH-PPV blended with C60-PCBM, C120-OPCBM and C60-MDHE, C120-O-MDHE under diode laser (532 nm) and Xe-lamp light excitation studied by means of X,W-band at temperatures 30–80 K is reported. Subsequent high frequency W-band ESR data demonstrate the reproducible, but variable effect of appreciable dispersion (D) contribution in the ESR spectral line for the di-fullerene anion radicals. It is suggested that the increase of theDpart relative to the absorption (A) in the summarized ESR absorption line in blends with difullerenes is caused by the higher value of difullerene medium conductivity. The obtained data are quantitatively discussed by the D/A~F(d/delta) functional dependence in approach of plane film geometry, wheredis the film thickness anddis the skin-depth. The influence of nu-dependent at D/A value has been checked using X-band LESR.