O’Sullivan is an experienced engineer who was previously Managing Director of the Airports Division at Heathrow Airport Holdings.
He will take over the chief executive post from Graham Dalton who announced his departure in January after 7 years leading the Highways Agency.
Highways England Chairman Colin Matthews said: “I am delighted to announce Jim’s appointment to lead Highways England in a new, challenging era.
“The government has committed to the biggest investment in roads in a generation: there are more than 100 roads schemes in its Road Investment Strategy which Highways England will be responsible for delivering to provide safer, more reliable and much improved journeys on our busiest roads.
“I would like to thank Graham Dalton for his leadership over the past 7 years.
“He has been responsible for significant improvement schemes, as well as meeting the needs of the nation during severe weather and events of international interest such as the 2012 Olympics, all culminating in the successful transition from the Highways Agency to Highways England.
Secretary of State for Transport Patrick McLoughlin said: “Jim’s experience of leading world-class infrastructure companies means I can be confident he will ensure that the benefits of the record investment this government is making in our roads delivers for drivers and businesses across the whole of the UK on time and on budget.
O’Sullivan will join on Monday 22 June 2015, before formally taking over from Graham Dalton on Wednesday 1 July 2015.