Here is a nice video with a collection of Top 10 most incredible and biggest jump ever made by man. The collection includes jumpers from buildings, towers, mountains to caves, but the most incredible and the only ever jump made from outter space belongs to Joseph Kittinger.
On August 16, 1960, he made the final jump from the Excelsior III at 102,800 feet (31,300 m). Towing a small drogue parachute for initial stabilization, he fell for four minutes and 36 seconds, reaching a maximum speed of 614 miles per hour (988 km/h) before opening his parachute at 18,000 feet (5,500 m). Pressurization for his right glove malfunctioned during the ascent, and his right hand swelled up to twice its normal size. He set historical numbers for highest balloon ascent, highest parachute jump, longest drogue-fall (four minutes), and fastest speed by a human being through the atmosphere. These are still current USAF records, but were not submitted for aerospace world records to the Fédération Aéronautique Internationale (FAI). Source: wikipedia.org