PSYCHE homonuclear decoupling, a prominent pure shift NMR method, is successfully applied to adulteration discrimination of honey and geographical originality identification of tea. Effects of homonuclear couplings are efficiently suppressed, producing resolution-enhanced spectra. The pair wise honey and tea samples are well separated in OPLS-DA models with high predictability. Due to the well-resolved and accurate assignment of singlet resonances after decoupling, PSYCHE is advantageous in the identification of differential components and accurate quantification of compound concentrations presented by enhanced volcano and Beeswarm plots of honey samples, while the analysis of NOESY is easily interfered by overlapped resonances, which is further proved by the STOCSY analysis, displaying the spectral stability and reproducibility. Experimental results show that PSYCHE can improve the spectral resolution of natural complex products such as honey and tea and be combined with multivariate statistical analysis and serve as a supplementary technique to the standard methods, especially for samples systems composed by a few high-content compounds.