The application of calcium- and magnesium-rich materials to soil, known as liming, has long been a foundation of many agro-ecosystems worldwide because of its role in counteracting soil acidity. Although liming contributes to increased rates of respiration from soil thereby potentially reducing soils ability to act as a CO2 sink, the long-term effects of liming on soil organic carbon (Corg) sequestration are largely unknown. Here, using data spanning 129 years of the Park Grass Experiment at Rothamsted (UK), we show net Corg sequestration measured in the 0–23 cm layer at different time intervals since 1876 was 2–20 times greater in limed than in unlimed soils. The main cause of this large Corg accrual was greater biological activity in limed soils, which despite increasing soil respiration rates, led to plant C inputs being processed and incorporated into resistant soil organo-mineral pools. Limed organo-mineral soils showed: (1) greater Corg content for similar plant productivity levels (i.e. hay yields); (2) higher 14C incorporation after 1950s atomic bomb testing and (3) lower C : N ratios than unlimed organo-mineral soils, which also indicate higher microbial processing of plant C. Our results show that greater Corg sequestration in limed soils strongly reduced the global warming potential of long-term liming to permanent grassland suggesting the net contribution of agricultural liming to global warming could be lower than previously estimated. Our study demonstrates that liming might prove to be an effective mitigation strategy, especially because liming applications can be associated with a reduced use of nitrogen fertilizer which is a key cause for increased greenhouse gas emissions from agro-ecosystems.