Objective:To investigate the clinical significance of plasma free metanephrines(MNs) in the diagnosis and prognosis of pheochromocytoma by high performance liquid chromatography-electrochemical detection(HPLC-ED). Methods:HPLC-ED was carried out to detect plasma free MNs,including 21 patients with pheochromocytoma,26 healthy volunteers,23 patients with primary hypertension and 24 patients with adrenal mass but without pheochromocytoma. Results:Plasma concentrations of free MNs in patients with pheochromocytoma were significantly increased compared with those of other groups(P<0.05). Taking normetanephrine(NMN) 150 ng/L and(or) metanephrine(MN) 120 ng/L as cut-off value,the sensitivity and specificity for diagnosis of pheochromocytoma were 100% and 89% respectively. Plasma concentrations of free MNs showed significant positive relationships with tumors size in patients with pheochromocytomas(NMN:r=0.952,P=0.000;MN:r=0.510,P=0.018). Plasma concentrations of free MNs in patients with pheochromocytoma dropped rapidly after the surgery. Conclusion:Plasma free MNs are good markers for the diagnosis and progno-sis of pheochromocytoma.