Captain James T. Kirk was a recipient of this medal in the mid-23rd century. Kirk's emotional reaction to seeing the medal, after removing it from the safe in his quarters, seems to have helped him shake off the effect of the Omicron spores. (TOS: "Court Martial", "This Side of Paradise")
Holodeck simulation - Captain Riker Edit
In 2367, while exploring a cavern on Alpha Onias III, Commander William T. Riker was rendered unconscious by gases. While unconscious, neural scanners scanned Riker's brain. The scanners used elements of Riker's reality and constructed a holodeck simulation with those elements interspersed throughout, so that it felt real to him. What Riker wanted, the scanners made possible.
In one of these simulations, on stardate 51692, at the conclusion of the Praetor Campaign, Captain Riker of the USS Titan was awarded the Starfleet Medal of Honor. In the campaign, the Titan detected and prevented a Romulan preemptive strike into the Gamma Hydra sector by the Romulans. In 2283, this award was mentioned in Riker's service record that was on display in his quarters on the Enterprise-D. (TNG: "Future Imperfect", okudagram)