In this work, we provide a holistic picture about the relationship between atomic structure, mechanical properties, and thermal stability of ZrCuAlx thin film metallic glasses (TFMGs) varying the Al content from 0 to 12 at. %, carrying out a broad characterization involving experiments and ab initio molecular dynamic simulations (AIMD). We show that the addition of Al resulted in a change of average interatomic distances by ~10 pm with the formation of shorter bonds (Al-Zr and Al-Cu), influencing the mechanical response (shear/elastic moduli and hardness) which increases by ~15% for 12 at.% Al. Moreover, tensile tests on polymer substrate revealed a maximum value for the crack initiation strain of 2.1% for ZrCuAl9, while the strain-to-failure rapidly decreases at higher Al contents. The observed reduction in damage tolerance is correlated to a transition in atomic configuration. Specifically, a maximum in density of full and defective icosahedral cluster population is observed at 9 at.% Al, inducing a more shear-resistant behavior to the material. Thermal stability is investigated by high energy and conventional x-ray diffraction and electrical resistivity measurements as a function of the temperature. Glass transition (Tg) and crystallization (Tx) temperature increase by Al addition reaching 450 and 500 ◦C, respectively for ZrCuAl12. The increase in thermal stability is related to the reduction in atomic mobility due to the formation of shorter chemical bonds, inhibiting atomic reconfiguration during crystallization. In conclusion, we provide guidelines to the design of compositional-tailored ZrCuAlx TFMGs with tuned mechanical properties and thermal stability with potential impact on industrial applications.