The singer, 36, was performing her latest single Miracle when the pyro flame went off at the wrong time and hit her square on.
The Hereford-born star was heard screaming and shouting “f**k” before running away from the pyro machine and then holding her face.
Goulding continued the performance and has yet to address the technical slip-up, but did take to Instagram shortly after her performance at the event, to share a shot of the crowd.
Elsewhere in her set, the Starry Eyed songstress put on an energetic show, performing a number of her greatest hits for 170,000 festival-goers, with the likes of Mumford & Son, Raye, and Kasabian also on the Victorious line-up.
The couple began dating in 2017 and tied the knot at York Minster four years ago following a year-long engagement.
Then, in August 2021, they welcomed their son Arthur.
Despite marriage woes, they are reportedly continuing to co-parent amicably.
Speaking about their separation, a source told The Sun that Goulding and Jopling have had “ups and downs for a while” but they “have always strongly felt they wanted to stay together so they could both be with their son.”