This paper describes the novel technique for determining constants in constitutive equation of elastic-plastic materials by the indentation test with indenters having different tip angles. FEM analyses were carried out to evaluate the effect of yield stress (σy), work hardening coefficient (A) and exponent (n) and indenter tip angle (θ) on the load-depth curve. The constitutive equation was determined from the characterized curves associated with the effects on the slope. Simulation analyses were performed for some material models to examine accuracy of the presented technique. The maximum discrepancy evaluated so far was 4% at most. It is confirmed that this technique is useful to determine the constitutive equation of a sub-surface of materials or coatings.