The company says it will offer the only app in the region, which covers areas including Cardiff, Newport and the Vale of Glamorgan, to offer customers the option of private hire vehicles and taxis on one platform.
The app will also be launching in Greater Manchester after obtaining licenses to operate in both areas.
It marks the company’s second international venture after launching in Australia in February.
Ben Legg, managing director in the UK, says Ola “looks forward to providing passengers with a dynamic, new, responsible service”.
He emphasised the firm’s screening processes for drivers and additional safety features such as 24/7 voice support and an option to share ride details with emergency contacts.
Ola unveiled its plans to launch in the UK earlier this month, and said it was working with local authorities to expand across the country by the end of 2018.
The app, which was founded in 2011 by Bhavish Aggarwal and Ankit Bhati, says it has 125 million customers in 110 cities around the world.
It enters the UK market as rival Uber faces increasing scrutiny and criticism.
Mayor of London Sadiq Khan is seeking powers to limit the number of Uber drivers in the English capital after a similar move in New York City.
In June, Westminster Magistrates’ Court overturned a ban on Uber imposed by Transport for London late last year and granted the firm a 15-month licence to operate in London.
Chief magistrate Emma Arbuthnot granted the reduced licence but criticised the firm for attempting to “grow the business, come what may”.
Ms Arbuthnot previously indicated the 18-month provisional licence Uber was requesting would be “too long” for her to grant.