Samsung said all three Chinese mobile carriers and all three South Korean mobile operators will begin Galaxy Note 4 sales on Friday.
Samsung's announcement marks the first time the Korean company has released a flagship smartphone in China before other markets.
Apple's iPhone 6 has yet to arrive in China, the world's most populous country. But Apple Inc still chalked up 10 million sales of the iPhone 6 and 6 Plus models in the first three days after the phones went on sale.
Apple's new iPhone 6 with its larger screen than previous models eliminates at key advantage for Samsung that lured buyers with the big screens of its Galaxy phones.
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The 4.7-inch screen of the iPhone 5 has been increased to 5.5-inches for the iPhone 6 Plus.
The Galaxy Note 4's display measures 5.7 inches diagonally, slightly larger than the biggest iPhone. The Note series comes with a stylus that Samsung calls "S Pen" for note taking and drawing.
US sales of the Galaxy Note 4 will start on Oct 17.
Samsung said the Galaxy Note Edge, which has a curved side screen that serves as a second screen to display weather information, clocks and menu buttons, will start going on sale in late October.