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Generation of accurate complex shaped products on various HSTR alloys is a key feature for many kinds of machine parts widely used in industries starting from biomedical to defence industries. However, producing these kinds of complex features using traditional processes face great challenges due to the thermo-mechanical effects. Being free of tool wear, thermal stresses and residual stresses, electrochemical machining (ECM) has the potential of machining of those materials. Electrochemical milling (EC milling) process is similar to conventional ECM in which metal is removed in a layer-by-layer fashion with simple geometric tool by moving a predefined path. Not only it is difficult to produce complex shaped products on various HSTR alloys but also it is almost impossible to predict the volumetric material removal prior to the production. So, in this paper, attempt has been made to develop a mathematical model for correlating the major process parameters with the responses of EC milling process. An empirical formula is obtained based on the model to predict the volumetric material removal for various complex shapes generation on Ti6Al4V. Thereafter, experimental verification is performed by electrochemical milling system and reveals good correlation with the theoretical predictions.