The Washington-based group brings governors and staff together to solve significant problems in the region.
The association asked President Barack Obama for federal help in January as the region's propane supply dwindled. Walker said in a statement Thursday that as chairman, he wants to start the propane conversation immediately.
Walker's administration has already eased regulations for propane drivers and made more state aid available to help low-income residents afford propane. The fuel's cost has increased with the shortage.
Walker becomes the fourth Wisconsin governor to chair the Midwestern Governor's Association. Former Gov. Jim Doyle led the nine-member group in 2007.