This study deals with diamond films grown via the microwave plasma-enhanced chemical vapor deposition technique (MWPECVD) on molybdenum (Mo) substrates of different roughness. This work is motivated by the necessity of overcoming the poor adhesion of diamond films on smooth Mo substrates, to ensure their effective application as cathodes for aerospace propulsion. The deposition process was monitored in situ using pyrometric interferometry (PI), thus enabling the real-time monitoring of both the rate and the temperature of deposition. The characterization of the obtained diamond films was performed using different techniques, such as Raman spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The poor adhesion of diamond films on Mo substrates was solved by roughening their surface, which promotes residual stress reduction in the diamond films. In this work, the PI technique was also exploited to support the prediction of the adhesion and stability of diamond films before their exposure in air through the monitoring of the deposition temperature. This represents a novel point of our work that has never been discussed in other research papers, as pyrometric interferometry is generally mainly used to assess the rate and the temperature of deposition.