A new class of substituted γ-amino alcohols and downstream pyrrolidine derivatives have been synthesized successfully from simple 1-phenyl-ethylamine, in which a representative all-substituted pyrrolidine derivative with multiple stereogenic centers was obtained by highly diastereoselective [1,2]-Wittig rearrangement and intramolecular cyclization with perfect chirality transfer (up to >99.9% de) and good yields.