In this letter we investigate the effects of varying the values ofxandyin (Pb1−xCux)Sr2(Y1−yCay)Cu2O7films deposited by laser ablation. The films are growninsituon (100) LaAlO3at the relatively low substrate temperature of 620 °C. The films are highly oriented with thec‐axis perpendicular to the substrate and exhibit a surface morphology which is unique to the oxide superconductors. By substituting Ca for Y it is possible to systematically vary the superconducting transition temperature from 10 K to a maximum of 86 K. On the other hand, variations in the value ofxseem to suggest that the film’s copper concentration in the (PbCu) plane can only exist within the narrow range of approximatelyx=0.2–0.3 and any extra copper added to the target ends up in an impurity phase.