While Clint Benedict was the first NHL goalie to wear a mask, as primitive as it was, but it was the great Jacques Plante who perfected and popularized the widespread use of facial protection in the National Hockey League and everywhere else, quite literally changing the face of hockey forever.
The Montreal Gazette's Dave Stubbs has a great article on the men behind Plante's first mask, Bill Burchmore and Al McKinney. The two men literally molded a NHL legend.
Burchmore was a sales and promotion manager at Montreal-headquartered Fiberglas Canada Ltd., and the inventor of the "phantom mask." But in order to make the mask, he first needed a mold of a face. Enter McKinney, an eager sales trainee. Burchmore plastered McKinney's face, although they forgot to apply a release agent, making the hardened plaster almost impossible to remove.
Once the mask was done, Burchmore approached Plante who began experimenting with the use of the mask. Soon enough he underwent his own face-molding in order to create his own mask. He would don the mask in a game in New York on November 1st, 1959. Soon he would replace the mask with the more famous pretzel mask.
And the rest, as they say, is history.
By the way, for a great look at the evolution of the goalie mask check out this hockey website from France: www.prohockeyfr.com. It's a great photo essay. I particularly enjoy the Johnny Bower window concept, shown to the right.