Current efforts to decarbonize the chemical sector by using captured CO2 and electrolytic H2 typically lead to high production costs and environmental collateral damage. Hence, there is a clear need to look for alternative, more efficient synthesis routes that could pave the way for a fully sustainable chemical industry. Bearing this in mind, here, we evaluate the economic and environmental implications of two low technology readiness level (TRL) novel single-step synthesis routes for acetic acid production using CO2 as a raw material: gas-to-acid methane carboxylation and semiartificial photosynthesis. Using process simulation and life-cycle assessment, we determine that these pathways, under a specific set of assumptions, could outperform the business-as-usual methanol carbonylation process at their current development state in terms of global warming, human health, ecosystem quality, and resource scarcity impacts, showing no signs of burden shifting. Furthermore, these routes also result in lower production costs derived from the reduced energy requirement associated with a single synthesis step. Overall, our preliminary results of the low TRL technologies based on experimental data highlight the potential economic and environmental benefits of exploring alternative synthesis routes, which could help bridge the current fossil-based industrial landscape to a more sustainable future.