We used X-ray spectroscopy as a diagnostic tool for investigating the properties of laser-cluster interactions at the stage in which non-adiabatic cluster expansion takes place and a quasi-homogeneous plasma is produced. The experiment was carried out with a 10 TW, 65 fs Ti:Sa laser focused on CO2 cluster jets. The effect of different laser-pulse contrast ratios and cluster concentrations was investigated. The X-ray emission associated to the Rydberg transitions allowed us to retrieve, through the density and temperature of the emitting plasma, the time after the beginning of the interaction at which the emission occurred. The comparison of this value with the estimated time for the “homogeneous” plasma formation shows that the degree of adiabaticity depends on both the cluster concentration and the pulse contrast. Interferometric measurements support the X-ray data concerning the plasma electron density.