An improved method is proposed to determine the content of 210Pb in lead using 210Po measured by alpha-ray spectrometry. This improved method, which is based on radiochemical separation by DDTC–toluene extraction, employs EDTA and citrate as masking reagents for the lead ions. To selectively extract polonium from an alkaline solution, the pH dependency was examined using a liquid scintillation counting method. And pH 9 was chosen as an extraction condition. Then 210Po was electrodeposited on a stainless steel disk, and the chemical recovery was followed by 209Po tracer. The effectiveness of the new method was validated by the agreement with the analytical results from five samples as determined by gamma-ray spectrometry.