The availability of genetic linkage maps enables the detection and analysis of QTLs contributing to quality traits of the genotype. Proton Transfer Reaction Mass Spectrometry (PTR-MS), a relatively novel spectrometric technique, has been applied to measure the headspace composition of the Volatile Organic Compounds (VOCs) emitted by apple fruit genotypes of the progeny ‘Fiesta’ × ‘Discovery’. Fruit samples were characterised by their PTR-MS spectra normalised to total area. QTL analysis for all PTR-MS peaks was carried out and 10 genomic regions associated with the peaks at m/z = 28, 43, 57, 61, 103, 115 and 145 were identified (LOD > 2.5). We show that it is possible to find quantitative trait loci (QTLs) related to PTR-MS characterisation of the headspace composition of single whole apple fruits indicating the presence of a link between molecular characterisation and PTR-MS data. We provide tentative information on the metabolites related to the detected QTLs based on available chemical information. A relation between apple skin colour and peaks related to carbonyl compounds was established.