X-ray line profile analysis (LPA) has been used for microstructural analysis of a Cu-1 wt.% Cr-0.1 wt.% Zr alloy. Using this technique, the stacking fault probability (SFP) and stacking fault energy (SFE) has been determined for the pure Cu and the Cu-1 wt.% Cr-0.1 wt.% Zr alloy. It is observed that there is an increase in the stacking fault probability (and corresponding decrease in stacking fault energy) in case of the alloy. The increased formation of faulted regions in the Cu-1 wt.% Cr-0.1 wt.% Zr alloy is supported by the observation of extended dislocation nodes and fringe contrast due to staking faults under TEM, and higher work hardening rate in the tension test. The high thermal fatigue resistance of this alloy is attributed to decrease in the stacking fault energy by addition of Cr and Zr to Cu.