We report here a direct knitting Method for preparation of highly robust, effective while air-and moisture-tolerant, and readily recyclable three-dimensional (3D) porous polymer-Pd network (PPPd) from the widely used Pd(PPh3)(4). Electro-beam induced Pd atom crystallization was observed for the first time in organic polymer and revealed the ultrafine dispersion of palladium atoms. Challenging types of Suzuki-Miyaura couplings, reductive coupling of aryl halides and oxidative coupling of arylboronic acid were successively catalyzed by PPPd in aqueous media. Also catalytically selective C-H functionalization reactions were achieved with orders of magnitude more efficient than conventional Pd homogeneous catalysts. The strategy developed here provides a practical method for easy-to-make yet highly efficient heterogeneous catalysis. (C) 2017 Elsevier Inc. All rights reserved.