Residual stresses, existed in engineering structures, could significantly influence the mechanical properties of structures. Accurate and non-destructive evaluation of the non-equibiaxial residual stresses in these structures is of great value for predicting their mechanical performance. In this work, investigating the mechanical behaviors of instrumented spherical indentation on stressed samples revealed that non-equibiaxial residual stresses could shift the load-depth curve upwards or downwards and cause the residual indentation imprint to be an elliptical one. Through theoretical, experimental, and finite element (FE) analyses, two characteristic indentation parameters, i.e., the relative change in loading curvature and the asymmetry factor of the residual indentation imprint, were found to have optimal sensitivity to residual stresses at a depth of 0.01R (R is the radius of spherical indenter). With the aid of dimensional analysis and FE simulations, non-equibiaxial residual stresses were quantitatively correlated with these two characteristic indentation parameters. The spherical indentation method was then proposed to evaluate non-equibiaxial residual stress based on these two correlations. Applications were illustrated on metallic samples (AA 7075-T6 and AA 2014-T6) with various introduced stresses. Both the numerical and experimental verifications demonstrated that the proposed method could evaluate non-equibiaxial surface residual stresses with reasonable accuracy.