Aryl sulfides play an important role in pharmaceuticals, biologically active molecules and polymeric materials. Herein, a general and efficient protocol for Pd@COF-TB (a kind of Pd nanocatalyst supported by a covalent organic framework)/DIPEA-catalyzed one-pot synthesis of symmetrical diaryl sulfides through a C-S coupling reaction from aryl iodides and Na2S2O3 is developed. More importantly, the addition of N,N-diisopropylethylamine (DIPEA) can not only enhance the catalytic activity of a Pd@COF-TB nanocatalyst, but also effectively inhibit the formation of biphenyl byproducts, which are a product of Ullmann reaction. Besides, it has been confirmed that the aryl Bunte salts generated in situ from Na2S2O3 and aryl iodides are the sulfur sources involved in this C-S coupling reaction. With the strategy proposed in this work, a variety of symmetrical diaryl sulfides could be obtained in moderate to excellent yields with a high tolerance of various functional groups. Moreover, a possible mechanism of this Pd nanoparticle-catalyzed C-S coupling reaction is proposed based on the results of controlling experiments.