: We investigate the bioelectricity potential of South Korea and the ramifications of the introduction of biomass use in electricity production for the Korean electricity market. The novelty of our study lies in that we consider a broad portfolio of biomass-energy technologies and carefully analyze their potential economic and environmental implications for South Korea given its biomass availability. To the best of our knowledge, this is the first study to attempt this in the context of South Korea. We first offer a preliminary assessment of South Korea’s theoretical biomass potential from forestry residues, livestock manure, and staple crops and of the amount of electricity that could be generated using these different biomass feedstocks. Our analysis suggests that biomass can be used to produce a substantial portion of the total electricity consumed annually in South Korea. In addition, out of all the feedstocks and technologies considered, pyrolysis of forestry residues could potentially impact the electricity market the most. Next, we simulate different bioelectricity supply shocks while randomly perturbing our model’s demand and supply elasticity parameters using the Monte Carlo methodology. Our results demonstrate that the introduction of bioelectricity could significantly affect South Korea’s electricity market as well as its CO2 emissions.