Pam Kramer has been charged with building the brand and increasing the five-year old social media platform's user base.
Simultaneously Twitter has appointed Joel Lunenfeld as director of global brand strategy to develop custom ad and partnership programmes for Twitter advertisers.
Lunenfeld joins from Moxie Interactive where he was chief executive. Kramer joins Twitter from GreenRoad where she was general manager of the consumer division. She has also previously held a number of chief marketing officer roles at companies including Lending club and MarketTools.
They will both report to Dick Costolo, Twitter chief executive, who said the new hires will help strengthen the way Twitter speaks to consumers and brands around the world.
The appointments come after Twitter co-founder Biz Stone recently announced he was taking a step back from the micro-blogging site to work on new projects, alongside its other co-founder, Evan Williams and Jason Goldman, former vice-president of product.
Twitter is currently looking to expand its advertising platform to UK-based brands and is setting up a new office in London, for sales and brand partnerships.