Solid phase micro-extraction (SPME) coupled with Gas Chromatography Mass Spectrometry (GC-MS) was used to extract and analyse the volatiles in the headspace above the plasmodial and sporulating stages of the slime mould Physarum Polycephalum. In total 115 compounds were identified from across a broad range of chemical classes. Although more (87) volatile organic compounds (VOCs) were identified when using a higher incubation temperature of 75oC, a large number of compounds (79) were still identified at the lower extraction temperature of 30oC and where the plasmodial stage was living. Far fewer compounds were extracted after sporulation at the two extraction temperatures. There were some marked differences between the VOCs identified in the plasmodial stage and after sporulation. In particular the nitrogen containing compounds acetonitrile, pyrrole, 2, 5-dimethyl-pyrazine and trimethyl pyrazine seemed to be associated with the sporulating stage. There were many compounds associated predominantly with the plasmodial stage including a number of furans and alkanes. Interestingly, a number of known fungal metabolites were identified including 1-octen-3-ol, 3-octanone, 1-octen-3 one, 3-octanol. In addition known metabolites of cyanobacteria and actinobacteria in particular geosmin was identified in the headspace. Volatile metabolites that had previously been identified as having a positive chemotactic response to the plasmodial stage of P. polycephalum were also identified including {\beta} farnesene, {\beta}-myrcene, limonene and 3-octanone. This study constitutes the first comprehensive analysis of the headspace volatiles emitted from Physarum Polycephalum. Further work to understand the origin and function of the volatiles identified is required
