Complex studies of the laser operated nonlinear optics for the BiFe0,9Cr0,1O3 and BiFe0,9Al0,1O3 multiferroics were performed for the first time. The studied materials were synthesized by the sol-gel process. Cr and Al doping changes significantly the second and third order nonlinear optical susceptibilities of BiFeO3. The FTIR spectra in the spectral range of 400-7800 cm(-1) were measured. It was studied dependences of the second and third order nonlinear optical effects versus the cationic substitution. The huge sensitivity of the nonlinear optics to the transition metals doping is explained by the influence of the highly polarizable cationic dopants on the output nonlinear optical susceptibilities and huge magneto-elecrtical coupling in the multiferroics materials.