The move will see the 28-year-old number eight link up with current Cherry and Whites' team-mate Alasdair Strokosch, who has also agreed a deal to join the Catalan club.
Narraway has spent his entire professional career at Kingsholm having made his debut towards the end of the 2002/03 season. He has gone on to make more than 150 appearances and was made club captain at the start of this season.
Narraway also won seven caps for England during his time at Gloucester, making his debut against Wales in 2008 with his most recent appearance coming in 2009 against Ireland at Croke Park.
Gloucester coach Bryan Redpath said in a statement: "Luke has signed for Perpignan and will be leaving us at the end of the season. He's been a fine player for Gloucester Rugby and I know has enjoyed the challenge of captaincy this season.
"He's been with us for a long time but it's the nature of the game that people move on to pastures new. I think he'll do well in France and will go with our best wishes.
"In the meantime, he'll be making the most of every moment in a Gloucester shirt and doing his bit to make this season as successful as possible."
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