Senior vice president Xiang Wang said Britain had a "cool" factor that aligned with the company's appeal to its customers.
"The UK is one of the important global centres for technology," he said in an interview ahead of the company's London launch.
"It is a young energetic place, so pretty much fits to our culture - we want to be the coolest company in our fans' minds."
Xiaomi, which listed in July and has a market value of about $44 billion, initially targeted other Asian markets for overseas expansion, notably India, where it toppled Samsung as the top smartphone seller earlier this year.
The company, founded in 2010, made its European debut in Spain a year ago - where according to research firm Canalys it already ranks third - followed by France and Italy this year.
It said in August that overseas revenue for the quarter ending June 30 had more than doubled year-on-year.
Xiaomi's UK product line-up is led by the Mi 8 Pro, which has a dual camera powered by artificial intelligence, a 6.21 inch high-definition AMOLED display, a pressure-sensitive in-display fingerprint sensor and a transparent glass back cover.
It is also bringing its entry-level Redmi 6A device, priced from 99 pounds ($130), Wang said, and some of the other products in the "Mi" range, including its Xiaomi Band 3 fitness band and an electric scooter.
The company's products will be sold both online and in store, including at an authorised Mi outlet due to open in London's Westfield mall on November 18.
"Online we will do mi.com and we will work with every online channel including Amazon and others," Wang said.
"Offline partners will include Carphone Warehouse and the exclusive launch carrier channel will be 3."
(Reporting by Paul Sandle; Editing by Jan Harvey)
By Paul Sandle