Around the year 1800, British inventor Thomas Wedgwood made the first known attempt to capture the image in a camera obscura by means of a light-sensitive substance. He used paper or white leather treated with silver nitrate. Although he succeeded in capturing the shadows of objects placed on the surface in direct sunlight, and even made shadow copies of paintings on glass, it was reported in 1802 that "the images formed by means of a camera obscura have been found too faint to produce, in any moderate time, an effect upon the nitrate of silver." The shadow images eventually darkened all over.

The first permanent photoetching was an image produced in 1822 by the French inventor Nicéphore Niépce, but it was destroyed in a later attempt to make prints from it.Niépce was successful again in 1825. In 1826 or 1827, he made the View from the Window at Le Gras, the earliest surviving photograph from nature (i.e., of the image of a real-world scene, as formed in a camera obscura by a lens)Because Niépce's camera photographs required an extremely long exposure (at least eight hours and probably several days), he sought to greatly improve his bitumen process or replace it with one that was more practical. In partnership with Louis Daguerre, he worked out post-exposure processing methods that produced visually superior results and replaced the bitumen with a more light-sensitive resin, but hours of exposure in the camera were still required. With an eye to eventual commercial exploitation, the partners opted for total secrecy.

Niépce died in 1833 and Daguerre then redirected the experiments toward the light-sensitive silver halides, which Niépce had abandoned many years earlier because of his inability to make the images he captured with them light-fast and permanent. Daguerre's efforts culminated in what would later be named the daguerreotype process. The essential elements—a silver-plated surface sensitized by iodine vapor, developed by mercury vapor, and "fixed" with hot saturated salt water—were in place in 1837. The required exposure time was measured in minutes instead of hours. Daguerre took the earliest confirmed photograph of a person in 1838 while capturing a view of a Paris street: unlike the other pedestrian and horse-drawn traffic on the busy boulevard, which appears deserted, one man having his boots polished stood sufficiently still throughout the several-minutes-long exposure to be visible. The existence of Daguerre's process was publicly announced, without details, on 7 January 1839. The news created an international sensation. France soon agreed to pay Daguerre a pension in exchange for the right to present his invention to the world as the gift of France, which occurred when complete working instructions were unveiled on 19 August 1839. In that same year, American photographer Robert Cornelius is credited with taking the earliest surviving photographic self-portrait.In Brazil, Hercules Florence had apparently started working out a silver-salt-based paper process in 1832, later naming it Photographie.