Coexisting scapolite, biotite and hornblende in scapolite-biotite rocks from the Tongmugou Pb-Zn deposit, Qinling, northwestern China are characterized by high levels of chlorine. Scapolite composition varies from EqAn27 to EqAn47 with 47–80 wt.% Cl. The scapolite composition is a sensitive indicator of the NaCl activity in coexisting hydrothermal fluid. Biotite contains 0.3–1.2 wt. % Cl and also has high F contents (0.2–0.7 wt.%). The hornblende is a Cl-rich hastingsite with Cl>3.5 wt.% and high (Na2O + K2O) contents (3.2–3.9 wt. %), high Xk [= K/(K + Na)] values (0.45–0.55) and high XFc [= Fe/(Fe + Mg)] values (0.76–0.79). The chlorine within these minerals is thought to be derived from evolved seawater. The scapolite-biotite rocks are products of Cl-rich alteration of volcanoclastic sedimentary rocks during submarine hydrothermal processes. Multiple-stage hydrothermal activity culminated with the circulation of a high-NaCl fluid that was also responsible for the formation of the massive sulphide deposits.