Decomposition and turnover of plant residues in soil play critical roles in the nutrient release and organic matter formation. Due to the deficit of high-resolution detection method, the characteristics and mechanisms of chemical structure of plant residues changing with climate, vegetation and soil conditions during their decomposition process remain unclear. Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool to elucidate direct information on chemical composition of nature organic matter. The recent progresses were reviewed in evaluating the quality of plant residues, predicting the decomposition rate and the transformation of functional groups of organic carbon, and analyzing the characteristics of soil humus by using the solid-state ¹³C NMR spectroscopy. To deepen our understanding of mechanisms of plant residue decomposition and organic matter formation, the composition and structure of biological macromolecules in plant residues should be comprehensively analyzed by using combined ?¹³C mass spectrometry and scanning electron microscopy. Then the decomposition pathway of functional groups of organic carbon could be studied at different temporal and spatial scales. And the synergetic change of microbial community composition and chemical structure of plant residues could be revealed by using high-throughput sequencing and gene chip methods. These will be helpful to put forwards the best management practices to promote the soil organic matter formation under different climate, soil and plant conditions.