## 1 Introduction  
The food industry is facing great challenges nowadays in developing natural antimicrobials and antioxidants for foods, responding to the growing consumer demand for safe, healthy and green foods, reducing the use of synthetic chemical preservatives. Food safety is an essential aspect to counteract the high incidence rates of foodborne diseases caused by pathogenic strains, including _Salmonella_, _Escherichia coli_, and _Listeria monocytogenes_, linked to the emergence of multidrug resistance to conventional antimicrobial agents [1]. Used as bio-preservatives and/or flavoring agents to improve the organoleptic properties of food products, herbs and spices are considered outstanding antioxidant and antimicrobial agents. This is the case of Mentha, Coriandrum, Cuminum, Capsicum and Foeniculum seeds, plants and spices [2, 3], frequently used in the formulation of traditional products in the Mediterranean region and North African countries [4, 5]. Based on toxicological research, the main phytochemical compounds of traditional spices and herbs are considered toxicologically safe [2]. In addition, several studies have reported a high correlation between antioxidant activity, antimicrobial efficacy and the level of bioactive components present in some herbs and spice preparations [3; 4]. Generally, crude extracts of herbs and spices consist of a large pool of phytochemicals, with the main bioactive compounds constituting up to 85%, while other components are found at trace levels [5]. Extracts and essential oils of Capsicum (_Capsicum annuum_ L.), belonging to the Solanaceae family, have also been used as a traditional medicinal alternative and are commonly recommended as antioxidant, antiseptic, antimicrobial, antifungal, aperitif, digestive, antispasmodic, anti-inflammatory and diuretic agents [6]. _Capsicum annuum_ L., a flowering plant, is widely cultivated for its hot and sweet chili peppers of its thousands of varieties and cultivar. The genus _Capsicum_ includes over thirty species, five of which (_C. annuum_, _C. frutscens_, _C. chinense_, _C. bacatum_, and _C. pubescens_) are domesticated and mainly grown for consumption [7]. The fruits of this species are common ingredients in the cuisines of many countries around the world and can also be grown for ornamental purposes or for medicinal uses [8]. Tunisian peppers are large, slightly curved pods, averaging 15-20 cm (6-8 inches) long, and have a conical shape that tapers to a pointed tip at the stemless end. The skin is shiny, waxy, hard and wrinkled and ripens from green to bright red. Beneath the surface, the flesh is thin, crisp, watery and pale red, enclosing a central cavity filled with small, cream-colored seeds. In particular, Paprika has a sweet flavor, while Baklouti, a pepper native to Tunisia in North Africa, has a unique and slightly spicy flavor. The peppers are available from summer to fall and are an excellent source of vitamin C, folate, vitamins A, B6 and E and potassium. These fruits are suitable for both raw and cooked applications such as roasting or stir-frying. The peppers can be sliced and tossed in salads, chopped into suaces and gravies, infused in oils for added flavor or dried and ground into a powder, and they are widely used to season and flavor various foods. Baklouti is a cultivar of chili pepper of the _Capsicum annuum_ species native to Tunisia and it is and is very popular with consumers as it is a medium-hot chili. In this study, for the first time, two _Capsicum_ accessions, Paprika and Baklouti, from Tunisia, were chemically investigated using a metabolomic approach based on two complementary techniques, such as Headspace Solid-Phase Microextraction-Gas Chromatography/Mass Spectrometry (HS-SPME-GC/MS) and Proton Transfer Reaction-Time-of-Flight-Mass Spectrometry (PTR-ToF-MS), to describe their volatile fraction. Further, GC/MS analysis on dry powders and extracts, after derivatization, was carried out to examine the non-volatile content.