Porous boron nitride is a new class of solid adsorbent with applications in CO2 capture. In order to further enhance the adsorption capacities of materials, new strategies such as porosity tuning, element doping and surface modification have been taken into account. In this work, metal-free modification of porous boron nitride (BN) has been prepared by a structure directing agent via simple heat treatment under N2 flow. We have demonstrated that textural properties of BN play a pivotal role in CO2 adsorption behavior. Therefore, addition of a triblock copolymer surfactant (P123) has been adopted to improve the pore ordering and textural properties of porous BN and its influence on the morphological and structural properties of pristine BN has been characterized. The obtained BN-P123 exhibits a high surface area of 476 m2/g, a large pore volume of 0.83 cm3/g with an abundance of micropores. More importantly, after modification with P123 copolymer, the capacity of pure CO2 on porous BN has improved by about 34.5% compared to pristine BN (2.69 mmol/g for BN-P123 vs. 2.00 mmol/g for pristine BN under ambient condition). The unique characteristics of boron nitride opens up new routes for designing porous BN, which could be employed for optimizing CO2 adsorption.