Anaerobic digestion (AD) has the potential to enhance the availability of nitrogen (N) from green manures; however, part of the sulfur (S) is lost with the biogas. In this study, the N and S availabilities from untreated and digested cover crop (CC) and straw mixtures were measured after application to soil in the laboratory. In addition, a microplot experiment was carried out to assess the N availability in a spring barley crop. A CC consisting of red clover (Trifolium pratense L.) and chicory (Cichorium intybus L.) was harvested and ensiled with barley straw (Hordeum vulgare L.) at different ratios (1:0, 10:1 and 3:1). The silages were either digested alone or co-digested with cattle manure (CM) in continuously fed anaerobic reactors. Six months after soil application, the net inorganic N release was − 7%, 15% and 25% of total N for untreated CC:straw ratios of 3:1, 10:1 and 1:0, respectively. AD significantly increased the net inorganic N release of these plant materials to 5%, 26% and 38% (mono-digestion) and 40%, 41% and 43% (co-digestion with CM). Results from the laboratory experiment corroborated the field experiment in which AD significantly increased the nitrogen fertiliser replacement value (NFRV) of the CC:straw from 19 to 41% of total N applied. Gaseous loss of S up to 30% was observed during AD while the total N content remained unchanged. Sulfate from untreated CC:straw and digestates was immobilised soon after application to soil, resulting in low availability of inorganic S. Digestion of CC and straw significantly reduced N immobilisation but clearly did not contribute to inorganic S supply.