Enhancing the molecular orientation of the regenerated silk fibroin (RF) up to a level comparable to the native silk is highly challenging. Our novel and promising strategy for the poststretching process is (1) creating at first an α-helix-HFIP complex with a hexagonal packing as an intermediate state and then (2) stretching it at a high temperature to induce the helix-to-sheet structural phase transition. Here we show for the first time the significantly high stretching efficiency of the proposed technique compared with the conventional wet-stretching techniques and the successful achievement of higher crystalline orientation and higher Young's modulus compared even with the native silk. The detailed structural analysis based on the time-resolved simultaneous measurement of stress-strain curve, synchrotron X-ray scatterings, and FTIR has revealed the structural transition mechanism from the hexagonally packed α-helix-HFIP complex to the highly oriented β-sheet crystalline state as well as the critical level of crystal orientation needed for the helix-to-sheet transition.