Covalent organic frameworks( COFs) enablep recise integration of variouso rganic building blocks into porouss keletons through topology predesign. Here,w e report the first example of COFs by integrating electron withdrawing bromine group onto the skeletons for triboelectricn anogenerators (TENG). The resulting framework exhibits high surface area and good crystallinity.T hus, the brominef unctionalizedC OF has more regular aligned p columns and arrays over the skeleton than bare COFs, which in turn significantly enhances chargetransport ability.A saresult, bromine functionalized COFs showed higher electrical outputp erformance at 5Hzw ith ap eak value of short circuit current density of 43.6 mAa nd outputv oltage of 416 V, which is 2a nd 1.3 times higher than those of bareC OFs (21.6 mAa nd 318 V),r espectively. These results demonstrated that this strategy for engineeringelectron withdrawingg roupso nt he skeleton could open an ew aspect of COFs for developing TENG devices.Triboelectricn anogenerators (TENG) are an ovel device that can effectively convert ambient mechanical energy,s uch as body motion, wind and vibratione nergy into electrical energy. [1] TENG has received increasing attention for harvesting mechanical energy because of their specific advantages,s uch as safety,s mall-size device, and easy fabrication. [2] As for TENG device, the current density ando utput voltage are the critical issuesf or its practical application. Furthermore, the frictional motions,t he environmental factors, especially the structure and functionality of the friction pair materials dominate the output performance of TENG device. [3,4] Although ab road diversityo fm aterials ranging from inorganic to organic have been employedt op repare TENG device, as ystematic and complex molecular design of these materials to manage the consecutive energy conversion process remainasubstantial challenging. [5] Covalent organic frameworks (COFs) are au nique class of crystalline porous materials, which are constructed from organic buildingu nits via reversible chemical reactions. [6] Since the seminal work reported by Yaghi and co-workersi n2 005, [7] great progress over the last decadew as achieved in the exploration of topology diagrams and synthetic reactions. [8][9][10] Benefiting from the features of designable regularp orous structures and versatile functionalities throught opologya nd building blocksd esign,C OFs have been regarded as one of the most promising materials in gas sorption [11,12] and separation, [13,14] sensing, [15] ion conductor, [16,17] catalysis, [18][19][20][21] energy storage, [13b, 22, 23] semiconductor [24, 25] and electronic devices. [26,27] In addition, another inherit advantage of COFs is their densely aligned p columns and arrayso ver the skeleton, which can be utilizedaspre-arranged pathways to facilitate charge transport. This distinct feature is hard to achieve from other inorganic and organic materials. Thus, COFs could offer an attractive structure-function platform for developing appropriate TENG...