A novel and efficient Pd/C-catalyzed Stille cross-coupling reaction of aryltriazenes with tributyl(phenyl)stannane has been realized in the presence of 1 equiv of BF3•OEt2 under room temperature. The Pd/C catalyst could be re-used several times and still retained its high activity. The present protocol, utilizes simple and recyclable catalyst, readily available starting materials and mild reaction conditions, provides an attractive methodology to a diverse range of biaryl products in moderate to excellent yields.