He will be responsible for developing and implementing the BEF’s communications and marketing strategies to support the administrator’s wider strategy.
Williams joins the federation following 20 years with the BBC as a sports journalist and most recently as a sports presenter on the BBC Radio 2 Drivetime Show with Simon Mayo, where they worked together for eight years, reaching an audience of more than six million people each week.
From 2006 to 2010, he was the sports presenter on BBC Radio 5 Live Breakfast with Nicky Campbell and worked at the Beijing Olympic Games, two FIFA World Cups and a number of UEFA Champions League finals.
"I believe strongly in the power of sport and storytelling. I believe there are many great stories to be told about equestrian sports," he said.
"Our elite riders lead the world, but millions of others and their support staff take part in this sport every week because they love it. I can’t wait to meet them and help tell their stories."
British Equestrian Federation chief executive Nick Fellows added: "His knowledge of the industry will be a huge asset to our communications strategy as we look to promote the values and benefits of equestrian sport. He is a clear and passionate communicator and is someone we believe will work well engaging with all of our stakeholders."
Williams begins his new role on 7 January.