Natural asphalt, containing more than 70 % carbon in molecular structure, is one of the newest and most promising sources for producing large quantities of different carbonaceous compounds. In this article, we report a systematic study of the synthesis of a new network from solid natural asphalt via coating natural asphalt sulfonic acid with oxalic acid. Then, CuI was doped on the NA@oxalic acid network and in fallow that ability as an effective, new, thermal and air-stable, heterogeneous, and reusable catalyst for Csingle bondN bond formations via cross-coupling reactions of guanidine nitrate with aryl halides was investigated. The shape and size of the heterogeneous NA-SO3H@Oxalic Acid-Cu were characterized by SEM, FT-IR, BET,EDX and TGA techniques. In addition, the ability of NA-SO3H@oxalic acid@CuI to catalyze cross-coupling reactions was compared to MOF-199. NA-SO3H@oxalic acid@Cu, as well as MOF-199, catalyzed coupling reaction of guanidine and aryl halides in short reaction times, high yields, and mild conditions.