The carbon stable isotope ratio (δ13C) is a valuable chemical parameter in the investigation of the geographic origin, quality, and authenticity of foods. The aim of this study is the evaluation of the feasibility of 13C-NMR (Nuclear Magnetic Resonance) spectroscopy to determine the carbon stable isotope ratio, at natural abundance, of small organic molecules, such as vanillin, without the use of IRMS (Isotope Ratio Mass Spectrometry). The determination of vanillin origin is an active task of research, and differentiating between its natural and artificial forms is important to guarantee the quality of food products. To reach our goal, nine vanillin samples were analyzed using both 13C quantitative NMR spectroscopy (under optimized experimental conditions) and IRMS, and the obtained δ13C values were compared using statistical analysis (linear regression, Bland–Altman plot, and ANOVA (analysis of variance)). The results of our study show that 13C-NMR spectroscopy can be used as a valuable alternative methodology to determine the bulk carbon isotope ratio and to identify the origin of vanillin. This makes it attractive for the analysis in the same experiment of site-specific and total isotope effects for testing authenticity, quality, and typicality of food samples. Moreover, the improvement of NMR spectroscopy makes it possible to avoid the influence of additives on carbon stable isotope ratio analysis and to clearly identify fraud and falsification in commercial samples.