Intra-Stark spectroscopy (ISS) is the spectroscopy within the quasi-static Stark profile of a spectral line. The present paper reviews the X-ray ISS-based studies recently advanced for the diagnostics of the relativistic laser–plasma interactions. By improving experiments performed on the Vulcan Petawatt (PW) laser facility at the Rutherford Appleton Laboratory (RAL), the simultaneous production of the Langmuir waves and of the ion acoustic turbulence at the surface of the relativistic critical density gave the first probe by ISS of the parametric decay instability (PDI) predicted by PIC simulations. The reliable reproducibility of the experimental signatures of PDI—i.e., the Langmuir-wave-induced dips—allowed measurements of the fields of the Langmuir and ion acoustic waves. The parallel theoretical study based on a rigorous condition of the dynamic resonance depending on the relative values of the ion acoustic and the Langmuir fields could explain the disappearance of the Langmuir dips as the Langmuir wave field increases. The ISS used for the diagnostic of the PDI process in relativistic laser–plasma interactions has reinforced the reliability of the spectral line shape while allowing for all broadening mechanisms. The results can be used for a better understanding of intense laser–plasma interactions and for laboratory modelling of physical processes in astrophysical objects.