Significance Chemical substitution is widely used to modify the charge-carrier concentration (“doping”) in complex quantum materials, but the influence of the associated structural disorder on the electronic phase behavior remains poorly understood. We synthesized thin films of the high-temperature superconductor L a 2 − x C a x C u O 4 with minimal structural disorder and characterized their doping levels through measurements of the optical conductivity. We find that superconductivity with T c = 15 to 20 K is stable up to much higher doping levels than previously found for analogous compounds with stronger disorder. The results imply that doping-induced disorder is the leading cause of the degradation of superconductivity for large carrier concentration, and they open up a previously inaccessible regime of the phase diagram of high-temperature superconductors to experimental investigation.