Ultrasmall nanocrystalline NiSm 0.01 Fe 1.99 O 4 and Ni 1−x Zn x Sm 0.01 Ga 0.5 Fe 1.49 O 4 (x = 0.0, 0.3, 0.5) ferrites were synthesized by sol-gel method. The effect of Ga and Zn substitution on the particle size and structural and magnetic properties was investigated using X-ray diffraction patterns (XRD), transmission electron microscope (TEM), Mössbauer effect spectroscopy (ME), and vibrating sample magnetometer (VSM) techniques. XRD measurements suggest the formation of single-phase spinel ferrites with ultrasmall particles size ranging from 4 to 8 nm. Mössbauer effect measurements show a clear signature of superparamagnetism in the studied samples, where the reduced particle size causes the broadening of the Mössbauer spectra and the presence of a pronounced central doublet in all the measured samples. VSM measurements show a strong reduction of saturation magnetization due to size effects.