Direct proof of use
U.S. Marine Corps OV-10 Broncos were fielded by Marine Observation Squadrons 1 and 2 during the 1990 Gulf War. The Marine Corps history Liberating Kuwait places two Bronco squadrons under Marine Aircraft Group 13 at King Abdul Aziz airfield, listing OV-10A and OV-10D+ aircraft in the group's Desert Storm order of battle.
On January 17, 1991, a VMO-1 OV-10 scouting the Saudi-Kuwaiti border spotted Iraqi artillery shelling al-Khafji and called for Marine AV-8B Harriers. The same Marine Corps University account says the OV-10 crew observed the effects of the strike, making the aircraft part of the first-day tactical air-control chain in the Marine sector.
Sources: Liberating Kuwait, The Desert War
Timeline
VMO-1 prepared twelve OV-10 aircraft for deployment after receiving Desert Shield orders in November 1990. Marine Corps Gazette authors Jason Breidenbach and Wayne Breakfield wrote that the first VMO-1 OV-10 arrived at King Abdul Aziz airfield in Saudi Arabia on January 17, 1991, and that the squadron flew its first Desert Storm mission less than 48 hours later.
VMO-2 had already sent six OV-10s on a long deployment to Saudi Arabia in August 1990. The Flying Leatherneck Aviation Museum states that VMO-2 flew 286 combat missions and 900 flight hours during Operation Desert Storm, with missions focused on controlling U.S. and allied artillery, attack aircraft, and naval gunfire.
Sources: The OV-10 - Marine Corps Gazette, Flying Leatherneck OV-10D Bronco
Narrative
The Bronco's Gulf War role centered on observation and forward air control rather than independent strike. Marine accounts describe VMO-1 providing continuous surveillance along the Kuwaiti-Saudi border, warning of Iraqi forces massing near Khafji on January 29, and coordinating close air support for Marine ground units along the border.
As the air campaign developed, Marine Corps University describes Marine direct-air-support control and forward air controllers airborne in OV-10s or UH-1s in the forward zone. It also describes artillery raids in which FAC-As in F/A-18Ds or OV-10s helped fix Iraqi firing positions for follow-on attacks by F/A-18s, AH-1s, or AV-8Bs.
During the February 1991 ground offensive into Kuwait, VMO-1 aircraft continued close support for the 1st and 2d Marine Divisions while flying under the oil-fire smoke layer. The Marine Corps Gazette account also records the loss of a VMO-1 OV-10 on February 25, 1991, while another crew was preparing to relieve it on station over Kuwait.
Sources: The OV-10 - Marine Corps Gazette, The Desert War