The German fashion house has become synonymous with McLaren since first sponsoring the team in 1981. Their logos have appeared on the title-winning cars of F1 legends Alain Prost, Ayrton Senna and Mika Hakkinen, and more recently Lewis Hamilton's victorious 2008 machine.
However the deal will end following the conclusion of the 2014 campaign.
"Hugo Boss has recently decided to co-operate with Mercedes-Benz on a number of international marketing projects unrelated to F1," said a McLaren spokesman.
"That being the case, it would be inappropriate for Hugo Boss to continue in partnership with an F1 competitor to Mercedes-Benz, however successful that partnership has been in the past and remains now."
The Brackley squad have already lured star driver Hamilton and technical chief Paddy Lowe away from McLaren, who will end their 20-year engine deal with the German marque at the end of 2014. The Woking-based team will switch to Honda power next year are expected to unveil a new title sponsor and corporate identity to distinguish themselves from the Silver Arrows.