In recent years pollution due to hydrocarbon spills has increased markedly as a result of the numerous advances in technologies and industrial processes. Anthropogenic activities (accidental or illegal) are responsible for most of these incidents. In some cases, the spills are not detected at the moment they occur and the contaminants are subjected to different degradation phenomena that may change the chemical composition of the hydrocarbon over time. An incorrect or ineffective identification of the spill could lead to significant consequences, bearing in mind that most spills are hazardous to the environment. In the present work the capacity of the analytical technique based on the Electronic Nose (eNose) combined with chemometrics in the identification and discrimination of different weathered petroleum-derived products (PDPs) was studied. Different volumes (40 μL and 80 μL) of PDPs (gasoline, diesel, and paraffin) were poured onto different supports (wood, cork, paper, and cotton sheet) and subjected to a natural weathering process by evaporation for one month. The porosity of the support was also studied. The application of linear discriminant analysis allowed the full discrimination of the samples according to the presence/absence of PDP and a 97.7% of correct discrimination of the different PDPs regardless of the weathering time, support or volume used. The results show that the system is capable of detecting and discriminating the presence of petroleum-derived products in any of the situations studied.