Wire electric discharge machining (WEDM) is a nontraditional machining process for machining conductive materials with complex and intricate shapes with a high surface finish and dimensional accuracy. The decision making for the selection of the best set of combinations of input process parameters is a major challenge. Therefore a proper optimization tool should be used for the optimal selection of process parameters. The resent work deals with the comparative study of Preferential Selection Index (PSI) and Technique for Order of Preference by Similarity to Ideal Solution (TOPSIS) for the selection of process parameters during machining of EN31 tool steel. Four input parameters- Pulse on Time (Ton ), Pulse off Time (Toff ), Servo Voltage (SV) and the Wire tension (WT) are considered. Surface roughness and material removal rate are the measured output responses. Taguchi L9 orthogonal array is used for developing the experimental design. Three levels of each control factor are considered. The results show that a single parameter alone does not have a significant influence on the output responses. Thequality of the output responses depends on the combination of the various set of input parameters. The best set of combination suggested from the current input parameters for machining of EN31 Tool Steel by Wire EDM Process is found to be Pulse on Time (Ton )= 15μs, Pulse Off Time (Toff )=35μs, Servo Voltage (SV)=40V and the Wire tension (WT)=5kgf from both PSI as well as TOPSIS techniques. Confirmation experiments are performed to validate the optimal results.