Multifunctionalization of microporous polymers is highly desirable but remains a significant challenge, considering that the current microporous polymers are generally hydrophobic and nonresponsive to different environmental stimuli and difficult to be carbonized without damage of their well-defined nano-morphology. Herein, we demonstrate a facile and versatile method to fabricate water-dispersible, pH/temperature responsive and readily carbonizable hairy microporous polymeric nanospheres based on combination of the hyper-cross-linking chemistry with the surface-initiated atom transfer radical polymerization (SI-ATRP). The hyper-cross-linking creates a highly microporous core, whereas the SI-ATRP provides diverse functionalities by surface grafting of hairy functional blocks. The as-prepared materials present multifunctional properties, including sensitive response to pH/temperature, high adsorption capacity toward adsorbates from aqueous solution, and valuable transformation into well-defined microporous carbon nanospheres because of hybrid of carbonizable core and thermo-decomposable protection shell. We hope this strategy could promote the development of both functional microporous polymers and advanced hairy nanoparticles for multipurpose applications.