Background: Postoperative hypocalcemia is one of the most common complications following parathyroidectomy for primary hyperparathyroidism (PHPT). The aim of this study was to analyze the predictive value of biochemical parameters as indicators for episodes of hypocalcemia in patients undergoing parathyroidectomy for PHPT., Methods: The patients with PHPT who underwent parathyroidectomy between February 2004 and February 2014 were studied retrospectively at a single medical center. The patients were divided into biochemical, clinical, and no postoperative hypocalcemia groups, based on different clinical manifestations. Potential risk factors for postoperative hypocalcemia were identified and investigated by univariate and multivariate Logistic regression analysis., Results: Of the 139 cases, 25 patients (18.0%) were diagnosed with postoperative hypocalcemia according to the traditional criterion. Univariate analysis revealed only alkaline phosphatase (ALP) and the small area under the curve (AUC) of receiver operating characteristics (ROC) curve for ALP demonstrates low accuracy in predicting the occurrence of postoperative hypocalcemia. Based on new criteria, 22 patients were added to the postoperative hypocalcemia group and similar biochemical parameters were compared. The serum ALP was a significant independent risk factor for postoperative hypocalcemia (P = 0.000) and its AUC of ROC curve was 0.783. The optimal cutoff point was 269 U/L and the sensitivity and specificity for prediction were 89.2% and 64.3%, respectively., Conclusions: The risk of postoperative hypocalcemia after parathyroidectomy should be emphasized for patients with typical symptoms of hypocalcemia despite their serum calcium level is in normal or a little higher range. Serum ALP is a predictive factor for the occurrence of postoperative hypocalcemia.