Blueberries (Vaccinium sp.) are consumed all around the globe, however, their endophytic community has not been thoroughly researched, specifically their fruit endophytes. We aimed to isolate and analyze easily cultivable blueberry fruit endophytes to help in future research, concerning probiotic microorganisms. Twelve strains were isolated in this pilot study, genetically homologous with Staphylococcus hominis, Staphylococcus cohnii, Salmonella enterica, Leuconostoc mesenteroides, and [Candida] santamariae. To determine the molecular composition of these isolates we used label-free surface-enhanced Raman spectroscopy (SERS). To our knowledge, this is the first time that SERS spectra for L. mesenteroides and C. santamariae are presented, as well as the first report of Candida yeast, isolated specifically from blueberry fruits. Our findings suggest that the differences in tested yeast and bacteria SERS spectra and subsequent differentiation are facilitated by minor shifts in spectral peak positions as well as their intensities. Moreover, we used principal component and discriminant function analyses to differentiate chemotypes within our isolate group, proving the sensitivity of the technique and its usefulness to recognize different strains in plant-associated microbe samples, which will aid to streamline future studies in biofertilizers and biocontrol agents.