The complicated superdislocation dissociation, dislocation core properties, and slip mechanism of L12 structural alloys have been controversial. Herein, the generalized stacking‐fault energy surfaces (γ‐surfaces) of the {001}, {110}, and {111} planes in L12‐Al3RE (RE = Er, Tm, Yb, Lu) compounds are first calculated according to ab initio density functional theory. Based on the γ‐surfaces, the superdislocation dissociation modes are preliminarily estimated using the unstable and stable stacking‐fault energies and their ratio. The result shows that the possible type of dissociations cannot be determined just from these ratios. Then, the 2D Peierls–Nabarro (PN) model is applied to simulate the ⟨110⟩{111} superdislocation dissociation configuration evolution in L12‐Al3RE, and the complete dislocation properties, including the dissociation width, the dislocation movement, and the Peierls energy and stress, are also investigated. The present study indicates that the combination of the γ‐surface and the 2D PN model can comprehensively elucidate the superdislocation properties and deformation mechanisms of L12 structural alloys.