The airline had placed a "firm order" for 10 777-9 passenger jets and four 777-8 freighter planes, which Boeing said were part of its "777X family".
China Airlines said it expected to start receiving the aircraft in 2030 and has the option to buy another nine.
"We value China Airlines' continued confidence and look forward to delivering the new 777Xs adorned with the beautiful plum blossom livery in the coming years," said Brad McMullen, Boeing senior vice president of commercial sales and marketing.
The companies did not provide the value of the order, which follows Taiwan President Lai Ching-te's repeated vows to buy more from the United States in a bid to avoid hefty tariffs.
US President Donald Trump last month slapped a 32 percent tariff on Taiwanese shipments before pausing the levies on Taiwan and other US trading partners for 90 days.
A global 10 percent tariff is still in place. Taiwan is seeking to reduce the tariffs to zero in ongoing trade talks with Washington.
China Airlines' order comes after Beijing backed out of a deal to buy new Boeing planes due to US tariffs imposed on Chinese products.
And it follows a turbulent year for the US aircraft maker, with production and quality control problems, lawsuits, corporate upheaval, increased regulatory oversight and a labour strike at a major factory.
Boeing announced in October the elimination of around 10 percent of its worldwide workforce, the discontinuation of the 767 Freighter in 2027 and the postponement of delivery of the first 777X to 2026.
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