The first proto-Techno/Electro release was Cybotron's 'Alleys Of Your Mind' in 1981. That same year, a group by the name of 'A Number Of Names' released another important and influentional song called 'Sharivari'. While both of those songs aren't pure Techno, they are the roots of the sound and a very important part of the history.
The term Techno (specifically relating to the music genre) was first used on the 1984 EP by Cybotron called 'Techno City'. It was also used on the 1988 compilation 'Techno! The New Dance Sound Of Detroit'. Juan Atkins, one half of Cybotron, was the first person to use the term to specifically describe the regional dance sound of Detroit. Atkins and the other purveyors of the sound - Derrick May, Kevin Saunderson, and Eddie Fowlkes - comprise what is known as 'The First Wave' (pre-1988).
Other notable early artists are Blake Baxter, James Pennington, and Anthony Shakir. The second wave of Techno artists, from 1988 onward, notably consisted of Jeff Mills, Mike Banks (of Underground Resistance), Carl Craig, Richie Hawtin, Rob Hood, Dave Angel, Kenny Larkin, Dan Bell, Drexciya, Stacey Pullen, Orlando Voorn, Kelli Hand, and Octave One (to name just a few).