The first goalie mask worn full time was in 1959 by Jacque Plante in the NHL. It was a homemade fiberglass mask similar to the one worn by the character Jason Vorhees in the movie series Friday the 13th. Other masks had been used for a short time on and off before then but were usually masks from other sports, such as the Fencing mask Elizabeth Graham used in 1927. In the 1970s the goalie mask changed into a cage/helmet combination which is still used by some lower level goalies (high school, college, recreational, etc) and has evolved into the fiberglass or Kevlar masks with a built in cage used by most goalies today in the NHL.
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The first mask was worn by the Montreal Maroons' Clint Benedict in 1930. He had suffered broken noses and fractured cheek bones and wanted to put an end to it.
All goalies wear masks (unless there's a distinction here between masks and helmets). In any case, the first goalie to wear a mask was Jacques Plante.