Staphylococcus simulans ZF4 and Lactobacillus plantarum SJ4 were screened from locally obtained food in Guizhou and then used to fermented pork loins. The effects of the starters on the quality of the fermented pork loins were explored through physicochemical analysis as well as E-nose and E-tongue assessments. High-throughput sequencing technology was used to reflect the distribution and function of the starters culture flora during the fermentation processes. The results showed that the starters conferred more well-rounded sensory qualities to the fermented pork loins, including improvements in their color, aroma, and other qualities. In addition, Corynebacterium variabile, Pediococcus pentosaceus, Lactococcus garvieae, Staphylococcus vitulinus, Bacillus velezensis, and Leuconostoc mesenteroides can be found to be inhibited by the starters (Staphylococcus simulans ZF4 and Lactobacillus plantarum SJ4), thereby improving safety of fermented pork loins. Moreover, throughout the fermentation process, Staphylococcus simulans ZF4 appeared to provide a stronger umami taste to the fermented pork loin, and the Lactobacillus plantarum SJ4 was better at producing flavor substances.