Gas fermentation aims to fix CO₂ into higher-value compounds, such as short or medium-chain fatty acids or alcohols. In this context, the use of mixed microbial consortia presents numerous advantages, including increased resilience and adaptability. The current study aimed to improve the performance of an enriched mixed microbial population via bioaugmentation with Megasphaera sueciensis and Clostridium carboxidivorans to improve the metabolite spectrum. The initial fermentation in trickle-bed reactors mainly yielded acetate, a low-value compound. Introducing M. sueciensis, which converts acetate into higher-chain fatty acids, shifted production toward butyrate (up to 3.2 g/L) and caproate (1.1 g/L). The presence of M. sueciensis was maintained even after several media swaps, showing its ability to establish itself as a permanent part of the microbial community. Metataxonomic analysis confirmed the successful integration of M. sueciensis into the mixed culture, with it becoming a dominant member of the Veillonellaceae family. In contrast, bioaugmentation with C. carboxidivorans was unsuccessful. Although this strain is known for producing alcohols, such as butanol and hexanol, it did not significantly enhance alcohol production, as attempts to establish it within the microbial consortium were unsuccessful. Despite these mixed results, bioaugmentation with complementary microbial capabilities remains a promising strategy to improve gas fermentation efficiency. This approach may enhance the economic feasibility of industrial-scale renewable chemical production.