Quantifying greenhouse gas (GHG) emission is important for evaluating various reduction measures for greenhouse gas, which causes significant negative impacts on earth. To estimate GHG emission from waste sector over the period of between 2000 and 2009 in Daejeon Metropolitan City, the 2006 IPCC (Intergovernmental Panel on Climate Change) and Korean GHG Inventory for local government guidelines and methodologies were employed. Four different waste treatment methods (landfill, incineration, biological treatment, and Sewage wastewater treatment) were evaluated to estimate GHG emission by following the guidelines. The trends of GHG emission rate by direct emission increased between 2000 and 2009 as a result of increased incineration rate. The solid waste sector was directly responsible for 307,700 tonCO2eq/yr in 2009. Incineration contributed approximately 57% of the GHG emission, while landfill disposal was responsible for about 30% of the GHG. Approximately 464,400 tonCO2eq/yr in 2009 was emitted by indirect emission from the waste sector. Based on the results, a variety of measures are needed to reduce the GHG emission from waste sector in Daejeon Metropolitan City along with implementing effective waste source reduction and recycling policy. More specifically, this evaluation proposed that among the possible reduction options, further source separation of recyclables as well as improved diversion of recyclable materials at proposed Daejeon resource recycling complex in 2014 would have the greater benefits for reducing GHG emissions in Daejeon Metropolitan City's waste sector.