The defect evolution associated with an anomalous work hardening behavior of a single crystalline quaternary Co-Al-W-Ta superalloy at 950 °C was investigated by transmission electron microscopy. As plastic deformation is initially confined to the γ matrix channels, a plateau arises in the stress-strain curve after yielding. At about 1% plastic strain, extensive shearing of the γ′ precipitates under superlattice stacking fault formation occurs leading to extreme work hardening rates up to 12 GPa and a total increase in stress of about 200 MPa. Additional investigations on the temperature and strain-rate dependence of the anomalous work hardening behavior reveal the significance of diffusion and segregation processes on the stress-strain curve and the work hardening behavior.