Sullivan claimed a seven shot victory in Hertfordshire to secure his fourth European Tour title of this career, top the UK Swing Order of Merit and climb into the top 100 of the Official World Golf Rankings as a result.
The 34-year-old will be in the company of the first winner of the six week UK Swing, which kickstarted European Tour golf's return to action after the global health crisis, during his first two rounds in Renato Paratore.
The Italian won the Betfred British Masters hosted by Lee Westwood at Close House Golf Course for his second European Tour title and will tee off at 08.39 alongside South African Brandon Stone, who comes into this event in good form following last week's tied for sixth finish.
Adrian Otaegui was Sullivan's closest challenger at Hanbury Manor Marriott Hotel & Country Club and will look to record another strong performance in Newport as he starts alongside fellow Spaniard Pablo Larrazábal and Hero Open champion Sam Horsfield at 12.40.
Home favourite and 2014 Ryder Cup star Jamie Donaldson has carded successive top 15 finishes heading to The Celtic Manor Resort and begins his first round 11 minutes earlier with Australian Scott Hend and Germany's Nicolai Von Dellingshausen.
Belgian Thomas Detry, who narrowly missed out on his first European Tour crown at the Hero Open, plays with American Kurt Kitayama - who finished tied for 51st at the US PGA Championship - and South African Justin Harding, teeing off at 13.02.
South African Wilco Nienaber, who finished fourth last week despite only being added to the field as a late replacement on Wednesday, will be joined by compatriot Zander Lombard for the first two rounds, with 2012 Ryder Cup star Nicolas Colsaerts, who posted a top ten finish in Ware, completing the threeball which tees off at 08.17.