Based in Luxembourg, he reports to Christina Smedley, global vice-president of comms for the eBay-owned payment brand, with a dotted line to the regional president Rupert Keeley.
Brooke joins from his position of global comms director, smart devices, at Nokia, which he took up three years ago following a stint as managing director of Harvard PR.
Brooke confirmed that Grayling had been added to PayPal's global roster. The move follows the appointment of MSL Group to look after the brand's North America region in March.
He stressed that Grayling is not PayPal's EMEA retained agency, but that the shop will be well placed to carry out future region-wide or country-specific comms work, as and when required.
It is understood that Grayling will be in line for work worth up to £3m.
Edelman's role as PayPal's retained agency in the UK is unaffected by the appointment.
Brooke said his new role would be focused on 'understanding the variety and appreciating the brand's different stages of maturing across each of the markets' within the EMEA region.
Brooke claimed PayPal has grown globally 30 per cent year on year, but that the brand has a varying presence across different jurisdictions.
He said the UK and Germany were ahead of other markets, offering a full range of PayPal products and services, whereas the brand was not fully established in other countries such as those within Eastern Europe.