Since the early 2000s, the European Union has increasingly prioritized policies aimed at combating social exclusion, with a focus on efficient fund allocation for social and sustainable cohesion objectives. Given the multidimensional nature of material deprivation, synthetic indicators are frequently employed in the literature to measure this phenomenon. However, these indicators often lack suitability for temporal analysis, which is crucial for understanding the persistence of disadvantaged statuses over time and the effectiveness of national and international policies. This article offers an innovative examination of the trends in material deprivation among European Union Member States during the period of 2005–2022. It provides a structured reconstruction of the phenomenon at the NUTS-1 level, within the context of the major economic and health crises that have characterized the 21st century. This study’s key innovation lies in the creation of a temporal index of material deprivation, employing the AMPI method, which incorporates a partially compensatory aggregative synthesis and allows for the monitoring of the phenomenon over time against a baseline year. This novel approach ensures the capability to analyze the evolution of material deprivation over time and across regions, with 2005 as the reference year. The findings reveal a general improvement in material deprivation levels compared to 2005, despite deteriorating conditions in the Mediterranean and Baltic regions. By maintaining 2005 as the reference year, this index facilitates the ongoing monitoring of the impacts of COVID-19 and the effects of national recovery policies, as well as the resilient and sustainable social policies promoted by the RecoverEU fund.