Recent environmental changes and socio-economic issues, required companies to adopt sustainability practices in order to safeguard the ecosystem on which insist and, at the same time, guarantying their profitability. In this scenario, the agri-food industry is particularly concerned, as food production and delivery have high impact on environment and society. Companies are investing in a digitization journey, surfing the flow of the transition from the actual technocentric vision of technology to a synergistic one involving social and environmental sustainability. Starting from these assumptions, the aim of this paper is to provide an overview of how the scientific literature explored the relationship between sustainability, Industry 4.0 (I4.0) and the agri-food sector, as well as delving into the role of the I4.0 pillars in driving sustainability moving toward Industry 5.0 (I5.0). A rigorous methodology guided the study toward a double-layers scientometric, performed with Bibliometrix. The sample was identified, using PRISMA methodology, in Scopus and WoS, leading to a database of 1114 papers and a further 9 sub-datasets, one for each I4.0 pillar. These datasets were analyzed in depth in order to recognize i) the main characteristics of the investigated research field; ii) the main research routes addressed in the investigated research field; iii) the current capability of each I4.0 pillar to drive sustainability in the investigated research field. The results reveal that the topic is recently and internationally debated; there is a strong interest in searching for sustainable solutions that safeguard natural resources with the help of data-driven technologies; among the I4.0 pillars, the simulation is the most recognized pillar in driving agri-food toward sustainability; the main topics addressed are linked to environmental and social domains. The study provides research and practical implications consisting of understanding the field concepts multiplicity, laying groundwork for future researchers, encouraging in the study replication, understanding how pursue sustainability issue, supporting the adoption of technology-based sustainable practices toward I5.0, stimulating in the exploration of new sustainability topics leveraging on technology application.