The flag carrier on Tuesday inaugurated its Dreamliner flight from Nairobi to Bangkok before continuing to Hong Kong, then back to Nairobi via the Thai capital.
It is also using the Dreamliner for its service from its hub at Jomo Kenyatta International Airport in Nairobi to Bangkok's Suvarnabhumi airport and onwards to Guangzhou.
Speaking at Suvarnabhumi on Tuesday, Kenya Airways' director of fleet and asset development Frederick Sine said the deployment of the state-of-the-art aircraft on the two routes would significantly enhance the experience of travellers.
It forms part of its fleet renewal programme that envisages acquisition of more Dreamliners and B777-300ER wide-body jets.
By the end of this year, Kenya Airways will have six of the nine Dreamliners it ordered in 2006 in its fleet alongside three B777-300ERs.
By 2021, Kenya Airways aims to operate 119 aircraft flying to 115 routes in 77 countries.
Through its hub in Nairobi, the airline now flies to 63 destinations worldwide.
"Besides increasing passenger appeal, this fleet renewal programme will also reaffirm our position as Africa's premier airline and the status as the airline with the youngest and most modern fleet on the continent," Mr Sine said.
Since 2003, Kenya Airways has flown from Nairobi to Bangkok, where it collects transit passengers from countries such as Indonesia, Australia, China and Japan who are bound for Africa.
Many of its passengers travelling via Bangkok are traders who visit Thailand and China to buy consumer goods for resale in Africa. Fewer than 10% of passengers are travelling for leisure.
The Dreamliner service between Nairobi and Bangkok is daily, with those extending to Guangzhou and Hong Kong operating four and three flights per week, respectively.
The Dreamliner is also used for services from Nairobi to Johannesburg and Paris.