The integration of passivating contacts based on a highly doped polycrystalline silicon (poly-Si) layer on top of a thin silicon oxide (SiO x ) layer has been identified as the next step to further increase the conversion efficiency of current mainstream crystalline silicon (c-Si) solar cells. However, the interrelation between the final properties of poly-Si/SiO x contacts and their fabrication process has not yet been fully unraveled, which is mostly due to the challenge of characterizing thin-film stacks with features in the nanometric range. Here, we apply in situ X-ray reflectometry and diffraction to investigate the multiscale (1 Å–100 nm) structural evolution of poly-Si contacts during annealing up to 900 °C. This allows us to quantify the densification and thinning of the poly-Si layer during annealing as well as to monitor the disruption of the thin SiO x layer at high temperature >800 °C. Moreover, results obtained on a broader range of thermal profiles, including firing with dwell times of a few seconds, emphasize the impact of high thermal budgets on poly-Si contacts’ final properties and thus the importance of ensuring a good control of such high-temperature processes when fabricating c-Si solar cells integrating such passivating contacts. Overall, this study demonstrates the robustness of combining different X-ray elastic scattering techniques (here XRR and GIXRD), which present the unique advantage of being rapid, nondestructive, and applicable on a large sample area, to unravel the multiscale structural evolution of poly-Si contacts in situ during high-temperature processes.