Present work comprises the use of different multivariate spectroscopic methods for tracking novel metabolomics signatures related to red wine chemistry. It is presented for the first time the proton nuclear magnetic resonance metabolomics fingerprint of a monovarietal Mexican Merlot, obtained with acquisition improvements recently proposed to the OIV Methods of Analysis sub-commission. Effective multi-presaturation solvent schemes have revealed a rich (poly)-phenolics aromatic region, so far not exploited for wine-fingerprinting or – targeted profiling routines. It is presented as well for the first time the use of simultaneous absorbance-transmission and fluorescence excitation-emission matrix “push-one-bottom” method (A-TEEMTM) at specific chemical conditions for a rapid, effective and high-sensitivity characterization of phenolic choreography in wines, as novel observables to quantify oenological practices and aging.