Colonel Redfield Proctor, previously of the 3rd and 5th Vermont regiments, was selected to command the regiment.
Ordered to retreat, the 5th Vermont regiment instead launched a bayonet charge, buying time for Union troops and the rest of the Vermont Brigade to fall back to their hasty works.
The 13th, 14th and 16th Vermont regiments played a pivotal role in the Union repulse of Pickett's Charge on the afternoon of July 3.
Colonel Asa P. Blunt, previously of the 3rd and 6th Vermont regiments, was selected to command the regiment.
During the next two weeks, the 4th and 5th Vermont regiments joined Smith's division.
On October 9, the Vermont regiments moved to Camp Griffin, about four miles from Chain Bridge.
After crossing the Emmitsburg Road, his brigade was hit by flanking fire from two Vermont regiments, driving it to the left and disrupting the cohesion of the assault.
The brigade as a whole took 439 casualties; the 5th Vermont regiment, commanded by Lt. Col. Lewis A. Grant, lost nearly half of its men, 209 of 428.
It was the longest serving Vermont regiment during the war.
The Vermont regiment suffered 65 casualties during the futile assault.