The effect of doping sodium on the growth process and properties of potassium hydrogen phthalate (KHP) single crystals by slow evaporation solution growth technique has been investigated. Incorporation of sodium into the crystalline matrix even in the presence of low dopant concentration in aqueous growth medium is well confirmed by energy dispersive X-ray spectroscopy and quantified by atomic absorption spectroscopy and inductively coupled plasma emission spectrometer (ICP) techniques. The FT-IR spectral analysis confirms the slight distortion of the structure of the crystals as a result of doping. The TG-DTA studies reveal the purity of the material and no decomposition is observed up to the melting point. Low Na-doping (10 mol%) slightly increases the second harmonic generation efficiency, whereas heavy doping {[KHP]:[Na] = 1:1} results in significant enhancement. It has also been found that the doping results in morphological changes.