The new service, Tmall World, will allow overseas Chinese users to buy goods from Alibaba's Tmall brand-to-consumer retail site, the company said in a statement.
"Alibaba will provide end-to-end solutions including logistics, payment, and localization support catering to each local market's needs," the statement said.
The firm plans on extending the Tmall World network to other countries in the future.
Alibaba has invested heavily in Southeast Asia, seeking to meet lofty user acquisition goals as the Chinese retail market shows signs of maturing.
Alibaba chairman Jack Ma told investors on Friday the company is aiming to have 2 billion customers within 15 years, with overseas customers accounting for 1.2 billion of those users.
Alibaba had roughly 450 million active annual buyers on its China marketplaces in the year ended March 31.
In 2016 it agreed to invest $1 billion in Southeast Asian retailer Lazada Group, and launching a service that allows local users to purchase a selection of Tmall goods.
The latest sales channels take aim at the 100 million Chinese citizens living overseas, and users must have an active Chinese payment method to purchase goods.
It comes as Alibaba payment affiliate Ant Financial is also expanding heavily in the region through investments and joint ventures.
In the past year the finance firm has sealed deals in Thailand, Indonesia, South Korea, Hong Kong and India, as well as rebranding Lazada Group's payment arm Hello Pay under Ant Financial's own Alipay brand.
It also comes as rival Chinese e-commerce firm JD.com Inc
On Friday JD.com Chief Executive Richard Liu told Reuters that the firm plans to launch services in Thailand by the end of the year, building on existing activities in Indonesia. - Reuters