Present numerical study examines the free convection heat transfer characteristics of supercritical water flow past a stretching sheet. A suitable equation for thermal expansion coefficient in supercritical fluid region is derived based on the equation of state approach (EOS) in terms of compressibility factor, pressure and temperature. In the present study Redlich-Kwong equation of state (RK-EOS) is used to calculate the thermal expansion coefficient in supercritical region. The values of thermal expansion coefficient calculated through RK-EOS lies close to the NIST data values when compared to the other equations of state like VW-EOS (Van der Waals equation of state) and Ideal gas-EOS. Also, the behaviour of Nusselt number is studied to characterize the heat transfer characteristics of supercritical water. However, the equations governing the supercritical fluid flow past a stretching sheet are coupled and nonlinear in nature. Hence, Runge-Kutta fourth-order integration scheme with shooting technique (RK-SM) is used to solve these equations. Numerical computations are performed for supercritical water (SCW) under the influence of various control parameters. Similarity solutions are obtained in terms of flow profiles in supercritical fluid region. Present study reports that, the normal velocity profile decreases and temperature field increases for the increasing values of reduced pressure and reduced temperature. Also, axial velocity profile shows the dual behaviour for the increasing values of unsteady parameter, reduced temperature and reduced pressure in the supercritical boundary layer region. Further, the component of normal velocity profile decays for the increasing values of unsteady parameter in supercritical fluid region. The calculated values of thermal expansion coefficient using Redlich-Kwong equation of state lies in the proximity of NIST data values when compared to Van der Waals and Ideal gas equations of state. Also, the local skin-friction coefficient decreases for the increasing values of reduced pressure and reduced temperature.