Predictions for oxidation behavior of Ni-base superalloys become more difficult than before because of the complex alloy composition. In this study, we focus on the initial oxidation behavior of Ni-base superalloys, and we suggest a new diagram to predict the initial oxide morphology of Ni-base superalloys with 63 binary, ternary, and multicomponent Ni-base single-crystal superalloys at 1373 K (1100 °C). As a comparison of observed and calculated weight changes after one cycle at 1373 K (1100 °C) obtained by a regression analysis, 63 alloys demonstrated two distinct behaviors, which are divided heretofore into group A and group B. Microstructural observation revealed that an oxide layer in the group A alloys consists of Al2O3 and/or spinel or complex oxide, whereas an oxide layer in the group B alloys consists of a thick NiO layer with an Al2O3 internal subscale. Thermodynamic properties can reflect more effects of alloy elements in Ni-base superalloys, and Al and Cr activities, calculated by Thermo-Calc, were used as factors to predict initial oxidation morphology. Groups A and B alloys can clearly be divided according to Al and Cr activities. This was suggested as a new diagram to predict the initial oxide morphology of Ni-base superalloys, and possibly it can apply for any generation of Ni-base superalloys.