Laura Barton in the MCU
She hadn't been mentioned or acknowledged prior to the events of Avengers: Age of Ultron in the Marvel Cinematic Universe (Earth-199999).
Laura Barton in the Comics
Laura Barton does appear in the Ultimate Comics Universe (Earth-1610), upon which the MCU is heavily based, as a matter of fact. From the Marvel Wikia:
Despite his dangerous, globe-spanning profession, Clint Barton managed to build a more stable family life than most of his peers, residing for years with his girlfriend Laura. She later became his wife, with whom he had three children: Callum, Lewis and baby Nicole, named after her godfather, Nick Fury. Hawkeye habitually phoned his family before every mission to say good-bye, just in case he never returned; but he always returned.
This matches almost perfectly MCU's Laura Barton, except their children are named Cooper, Lila, and Nathaniel Pietro. Much like in the Ultimate Universe, the Bartons' younger child is named in honour of Clint's friends/colleagues: Nathaniel is the masculine form of Natasha (in honour of Natasha Romanoff, the Black Widow), and Pietro is the first name of Quicksilver (Pietro Maximoff), who
was killed when he saved Hawkeye and a child from being struck by gunfire, during the climactic battle with Ultron in Sokovia.