Through the initiative, the US coffee chain hopes to reduce waste and encourage the uptake of renewable cups.
In the three-month trial, consumers who use takeaway cups in 35 selected London branches will have to pay an extra 5p, with proceeds from the levy to be donated to environmental charity Hubbub.
The company will also offer customers drinking in store ceramic cups in a bit to cut paper further.
In the UK around 2.5bn takeaway coffee cups are thrown away every year.
Many of these disposable cups are difficult to recycle as they often feature a thin plastic lining to make them watertight and the paper is often contaminated by coffee or tea.
"We're hoping that this charge will remind customers to rethink their use of single-use plastic-lined cups, as it has with plastic bags," said Simon Redfern, vice-president of communications at Starbucks Europe.
"We've offered a reusable cup discount for 20 years, with only 1.8 percent of customers currently taking up this offer, so we're really interested in working with Hubbub to see how this charge could help to change behaviour and help to reduce waste."
The ‘latte levy’ is the latest offensive in the war against plastic.
Many major players in the food and beverage industry are also trying to improve sustainability practices and reduce plastic waste
Pret A Manger announced that it was doubling its discount for customers who bring reusable cups into stores to 50p, in a bid to reduce the number of paper cups that are discarded as waste.
Meanwhile, the UK's largest coffee chain Costa Coffee also launched an in-store recycling scheme which aims to ensure that as many of its own takeaway cups - and those from its competitors are recycled.