Efforts to enhance greenhouse gas (GHG) emission reduction in East Asia play a pivotal role on both global and regional scales in advancing climate mitigation strategies. This study aimed to better constrain anthropogenic CO2 emission estimates by expanding the network of near-surface in-situ stations for CO2 observations across South Korea. To achieve an optimal CO2 network design, we conducted an Observing System Simulation Experiment (OSSE) coupled with the Stochastic Lagrangian Transport model (STILT), utilizing meteorological data from the Korean Integrated Model (KIM). Our inversion setup incorporated two CO2 emission datasets with a 0.1o resolution: EDGAR v6 for prior emissions and GRACED for truth emissions. A uniform model-mismatch error of 3 ppm was introduced across sites. The effectiveness of the existing five in-situ stations, termed the base network, in South Korea was evaluated to gauge their ability to constrain CO2 surface flux estimates. However, the findings revealed a reduction in flux uncertainty of only 29.2%, which fell short of the desired uncertainty reduction goal. In this base network, the Lotte World Tower (LWT: 37.5126°E, 127.1025°E) in Seoul and the Anmyeondo (AMY: 36.538576° N, 126.330071° E) site in Taean county stood as major contributors, with estimated reductions of 17.48% and 6.35%, respectively. Consequently, we proposed and developed an extended network, identifying seven candidate sites based on consideration of logistical factors, existing infrastructures, and proximity to the emission source regions. An incremental optimization scheme ranked their contributions, resulting in an additional 25% reduction, bringing the total to 54.13%. However, it is noteworthy that diminishing returns (ranging from 13% to less than 0.1%) were observed with an increase in station count mainly due to the possibility that adding a station earlier in the sequence might render subsequent stations redundant. Despite this, the proposed CO2 network successfully reduced uncertainty in emissions, narrowing the gap with the objectives of the Global Greenhouse Gas Watch (G3W). •Designing CO2 near-surface observation network over South Korea.•New stations selected considering logistic factors, existing infrastructures, and proximity to emission sources.•The base network was able to reduce 29.18% of the uncertainty in CO2 emissions.•Extending network, by adding new seven candidate sites, led to a total uncertainty reduction of 54.13%.