In 1914, Shackleton signed Hurley as photographer for his British Imperial Trans-Antarctic Expedition and formed the Imperial Trans-Antarctic Film Syndicate Ltd. to raise funds from the sale of Hurley's still photographs and motion pictures.

When the Endurance sailed in October 1914, Hurley carried a range of cameras, including a Cinematograph motion-picture camera, a square bellows stand plate camera, a Kodak Folding Pocket Camera Model 3A, and a Vest Pocket Kodak camera. The crew was astonished by the lengths to which he would go for an image, from high in the ship's rigging to the back of a dogsled; First Officer Lionel Greenstreet called him a "warrior with a camera [who] would go anywhere or do anything to get a picture." Hurley not only had the stamina to haul his cameras to the mountaintop of Duse Fell on South Georgia, but also was a talented artist and innovator. He was a pioneering practitioner of color photography with the Paget color process, and, when the long polar nights descended, he used multiple magnesium flares and long exposure times to capture images of the Endurance beset in darkness.

After they abandoned the debilitated Endurance, Shackleton ordered the crew members to pare their personal possessions down to two pounds each. Hurley had to leave his precious cameras behind, but Shackleton allowed him to keep a selection of photographs and motion-picture footage. Stripped to the waist, Hurley dove into the icy waters to retrieve his treasured images from the sinking wreck of the ship. Together, Shackleton and Hurley chose 120 glass plates to keep and smashed about 400; Shackleton feared that Hurley would endanger himself to return for them later. Hurley sealed the plates in metal tins with improvised solder, along with prints he had developed on board the ship. Hurley documented the remainder of their odyssey with only a handheld Vest Pocket Kodak camera and three rolls of film.

In 1917, Hurley returned to South Georgia on a new filming expedition. In 1919, his motion-picture footage of the Endurance expedition was released in the film In the Grip of the Polar Pack, which quickly became a critical and popular success. His photography also gained a wide audience when Shackleton featured it in his lecture tours.

In the years that followed, Hurley was attached to the Australian Imperial Force as its official photographer, documenting the battles of World War II. After the war, he traveled extensively on photographic expeditions, ranging from Tasmania to Papua New Guinea to Palestine and back to his native Australia. In 1948, he published Shackleton's Argonauts. He died on January 16, 1962.

Hurley's work from the Endurance expedition has been well preserved, and many of these images are seen in Shackleton's Antarctic Adventure. South, featuring Hurley's original 35mm cinematography of the Endurance expedition, was restored and re-released by the British Film Institute in 1998. Since 1929, the Royal Geographical Society in London has been curator of Hurley's original glass plate negatives. Original Hurley prints are held by the Scott Polar Research Institute in Cambridge, England, and The Macklin Collection in Aberdeen, Scotland. In addition, Hurley's Paget color glass transparencies are held by the Mitchell Library of the State Library of New South Wales in Sydney, Australia.