The proton transfer – time of flight – mass spectrometer (PTR-TOF-MS) is an innovative tool that enables the real-time separation and quantification of volatile organic compounds (VOCs) in complex gas mixtures, from trace levels up to parts per million, with a low fragmentation level due to a low-energy chemical ionization approach. The key advantages of this instrument, that have considerably boosted its use in a wide range of fields (including in food science and technology), are: (1) an unprecedented number of VOCs can be measured simultaneously with very high time resolution within a large dynamic range and (2) there is no need for pretreatment of the sample. The aim of the present work is to make an objective evaluation of the efficiency of PTR-TOF-MS approach for food characterization and valorization. Accordingly, a wide range of experimental applications are given: from the assessment of the optimal harvest time of olive oil fruits to the qualitative discrimination of saffron from different geographical origins, from the controlled designation of origin of truffles to the assessment of biodynamic farming effects on apple aroma, from the VOCs profiling during shelf-life of table fruits to the fingerprinting of diverse plant species. Results highlight PTR-TOF-MS as a high analytical throughput and non invasive tool, particularly suited to online analysis of dynamic flavor released from diverse food matrices along the food-to-fork production chain (i.e., from plants and crops to food processing and storage and, eventually, during food consumption) and capable of providing fingerprint for agro-industrial product characterizations.