Agrivoltaics’ share of renewable generation is relevant for countries to achieve their energy transition targets. Agrivoltaics is the dual and synergistic use of the land by agricultural crop production and photovoltaic (PV) systems. For their development around a country, a fundamental step is to determine which areas are suitable. This research work has developed a methodological framework for a reliable agrivoltaic land eligibility analysis at regional scale based on a spatial multicriteria analysis (i.e., GIS/MCDM-AHP). The challenging step has been to select a set of relevant criteria, also based on experts’ knowledge, able to capture the factors that can affect both the solar PV potential and agriculture-oriented factors. On the basis of these criteria, properly weighted, a 30 m-resolution land eligibility map for agrivoltaic systems has been generated for the NUTS-2 regions of Italy. We have found that Italy has an eligible area of 10.7 million hectares and a capacity potential of 6435 GW, assuming an installed power density of 0.6 MW/ha. Thus, a land coverage of only 1.24% of this area would allow to reach the national 80 GW target of new renewable capacity to achieve the country’s decarbonisation and energy transition objectives by 2030. The potential of installed capacity results at GW scale for the main land categories of arable land and permanent crops if they are just covered by only 5% with agrivoltaic systems. Thus, the impact of agrivoltaic systems development on land occupation can be considered marginal especially in relation to benefits generated for both the energy and agricultural sectors. Such a method is essentially targeted to regional authorities for planning the sustainable development of agrivoltaic systems at the local level.