Nano-sized NiFe2O4 powders were synthesized by sol–gel auto-combustion method using pH values from 7 to 9 in the sol. The effect of pH variations on complexing behavior of the species in the sol has been explained. Changes in phase constituents, microstructure and magnetic properties by changes in pH values were evaluated by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and vibration sample magnetometer (VSM) techniques. Changes in pH value from 7 to 9 changes the amounts of NiFe2O4, FeNi3 and α-Fe2O3 phases. Calculated mean crystallite sizes are in the range of 44 to 51nm. FESEM micrographs revealed that increasing the pH value to 9 causes formation of coarse particles with higher crystallinity. Saturation magnetization was increased from 36.96emu/g to 39.35emu/g by increasing pH value from 7 to 8 which is the result of increased FeNi3 content. Using higher pH values in the sol reduces the Ms value.