The earliest fictional robots and androids in film listed on Wikipedia are:
The Dummy, played by Ben Turpin in the silent short A Clever Dummy, dating from 1917, when the term "robot" did not yet exist.
-> Doesn't count: the Dummy was made to replace a postman.
The Mechanical Man from the silent film of the same name (1921)
-> Doesn't count: the Mechanical Man doesn't look like a human.
Maria/Futura, the Maschinenmensch – a robotic gynoid, played by German actress Brigitte Helm in both her robotic-appearing and human-appearing forms—from Metropolis, the silent science fiction film by famed Austrian-German director Fritz Lang (1927)
-> Might count: the Maschinenmensch had both human and robotic forms.
Going down the list, the next human-looking androids are:
- Sexbots or Fembots, including Robot # 11 (Diane) in Dr. Goldfoot and the Bikini Machine (1965) and Dr. Goldfoot and the Girl Bombs (1966)
And the first on the list that specifically mentions androids is:
- The robotic gunfighters and other androids in Westworld, one of which was played by Yul Brynner (1973)
It's interesting that androids don't really show up in movies until relatively late compared to books, as it's much easier to show a normal-looking human and claim it's a robot underneath than these clunky looking mechanical robots. But perhaps there wasn't much fun doing it that way, and perhaps audiences would have felt cheated.