Morrison, who was last month named HR director of the year at HR magazine's 2013 Excellence Awards, takes up the position with immediate effect and will report to CEO Tim Weldon.
Morrison was previously group HR director for the UK and International operations of The Random House Group. He was the Random House UK and Rest of World HR lead on the pre-merger team.
Tom Weldon, CEO Penguin Random House UK, said: "[Morrison] is passionate about HR, people and culture and how HR strategy can deliver improved business results and I am excited about the great programmes and initiatives we will be able to deliver."
Morrison said: "Penguin Random House is full of some of the most talented people I've had the pleasure of working with.
"Together we want to create a new organisation, building on the strong heritage of both Penguin and Random House that delivers future success for everyone involved."
Penguin Random House was established in July following the successful merger of publishing powerhouses Penguin and Random House creating a global general book publisher.