Cucumis melo fruit is highly valued for its sweet and refreshing flesh, however the flavour and value are also highly influenced by aroma as dictated by volatile organic compounds (VOCs). A simple and robust method of sampling VOCs on polydimethylsiloxane (PDMS) has been developed. Contrasting cultivars of C. melo subspecies melo were investigated at commercial maturity: three cultivars of var. Cantalupensis group Charentais (cv. Cézanne, Escrito, and Dalton) known to exhibit differences in ripening behaviour and shelf-life, as well as one cultivar of var. Cantalupensis group Ha’Ogan (cv. Noy Yisre’el) and one non-climacteric cultivar of var. Inodorus (cv. Tam Dew). The melon cultivar selection was based upon fruits exhibiting clear differences (cv. Noy Yisre’el and Tam Dew) and similarities (cv. Cézanne, Escrito, and Dalton) in flavour. In total, 58 VOCs were detected by thermal desorption (TD)-GC–MS which permitted the discrimination of each cultivar via Principal component analysis (PCA). PCA indicated a reduction in VOCs in the non-climacteric cv. Tam Dew compared to the four Cantalupensis cultivars. Within the group Charentais melons, the differences between the short, mid and long shelf-life cultivars were considerable. 1H NMR analysis led to the quantification of 12 core amino acids, their levels were 3–10-fold greater in the Charentais melons, although they were reduced in the highly fragrant cv. Cézanne, indicating their role as VOC precursors. This study along with comparisons to more traditional labour intensive solid phase micro-extraction (SPME) GC–MS VOC profiling data has indicated that the high-throughput PDMS method is of great potential for the assessment of melon aroma and quality.