Here is the ranking of the largest territory in ancient China.

1st largest:

Yuan Dynasty (about 13.72 million km2)

2nd largest:

Qing Dynasty (about 13.16 million km2)

3rd largest:

Tang Dynasty (about 12.51 million km2)

Hence, the answer should be Yuan Dynasty (AD1271-1368).

More trivia:

The Yuan dynasty (Chinese: 元朝; pinyin: Yuán Cháo), officially the Great Yuan, was a successor state to the Mongol Empire after its division and a ruling dynasty of China established by Kublai Khan, leader of the Mongol Borjigin clan, lasting from 1271 to 1368. In Chinese historiography, this dynasty followed the Song dynasty and preceded the Ming dynasty.

More Info: en.wikipedia.org