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According to the U.S. Census Bureau, the county has a total area of 578 square miles (1,500 km2), of which 576 square miles (1,490 km2) is land and 2.0 square miles (5.2 km2) (0.4%) is water. It has a humid continental climate (Dfa/Dfb) and average monthly temperatures in Waynesburg range from 28.9 °F in January to 71.9 °F in July. 
There were 14,724 households out of which 29.3 percent had children under the age of 18 living with them, 51.5 percent were married couples living together, 10.9 percent had a female householder with no husband present, and 32.3 percent were non-families. 27.0 percent of all households were made up of individuals and 11.7 percent had someone living alone who was 65 years of age or older. The average household size was 2.42 and the average family size was 2.91.
In the county, the population was spread out with 19.9 percent under the age of 18, 9.9 percent from 18 to 24, 25.5 percent from 25 to 44, 29.3 percent from 45 to 64, and 15.3 percent who were 65 years of age or older. The median age was 41.1 years. For every 100 females there were 106.2 males. For every 100 females age 18 and over, there were 105.6 males.
As of November 7, 2017, there were 21,671 registered voters in the county. Democrats hold a majority of 3,621 voters (16.71%); there was 11,659 registered Democrats, 8,038 registered Republicans, 1,858 voters registered to other parties, 64 to the Libertarian Party and 52 voters registered to the Green Party.
Map of Greene County, Pennsylvania with Municipal Labels showing Boroughs (red), Townships (white), and Census-designated places (blue).
Under Pennsylvania law, there are four types of incorporated municipalities: cities, boroughs, townships, and, in at most two cases, towns. The following boroughs and townships are located in Greene County:
Census-designated places are geographical areas designated by the U.S. Census Bureau for the purposes of compiling demographic data. They are not actual jurisdictions under Pennsylvania law. Other unincorporated communities, such as villages, may be listed here as well.