The article highlights the results of a comprehensive assessment of the productivity and sequestration potential of winter catch crops and post-harvest soybeans in the conditions of the Western Forest-Steppe of Ukraine. The study is aimed at substantiating the possibilities of increasing the efficiency of arable land use by obtaining two crops during the year and simultaneously reducing the concentration of carbon dioxide in the atmosphere. In the context of global climate change and increasing pressure on the agricultural sector, the search for agricultural technologies that can combine feed production with ecosystem services, in particular carbon absorption and accumulation, is of particular relevance. The sequestration potential of crops was assessed based on yield indicators and the yield of absolutely dry biomass, taking into account both above-ground and underground parts of plants. Field studies were conducted in 2022–2023 in the Ternopil region. It was established that the cultivation of hybrid winter rye Prokhas F1 in a system with post-harvest soybeans does not lead to a decrease in soybean productivity and provides a significant increase in the total yield of organic matter per unit area. The average yield of the above-ground mass of winter rye in terms of absolutely dry matter was 8.86 t/ha. Taking into account surface and root residues, the share of which for annual grasses was estimated at about 20% of the above-ground mass, the total yield of dry biomass reached 10.6 t/ha. This level of biological productivity indicates an intensive accumulation of organic matter and a high potential for binding atmospheric carbon. The results obtained confirm the feasibility of using winter catch crops as an important element of the adaptation of agricultural systems to climate change. Their implementation contributes to increasing the feed base, optimizing the use of the growing season, enriching the soil with organic matter, and enhancing carbon sequestration processes, which generally increases the ecological and economic sustainability of agroecosystems.