Optical pure α, γ‐disubstituted γ‐butyrolactones moieties are versatile building blocks for the synthesis of many drugs and natural products. Herein we report a straightforward and efficient approach to afford a series of chiral α, γ‐disubstituted γ‐butyrolactones with excellent results (up to 98 % yield, up to >99 : 1 d.r., and up to >99 % ee) through the double asymmetric hydrogenation of the (E)‐2‐methyl‐4‐oxo‐2‐alkenoic acids utilizing the rhodium/JosiPhos catalytic system.