This work reports a new synthesis strategy called hard-template synthesis to create hierarchical pores in porous organic framework materials. Two different mesoporous silicas (SBA-15 and B56-E-20) were used as the hard templates and biphenyl was employed as the single organic precursor. PAF-45 was prepared by in situ coupling biphenyl within the voids of mesoporous silica. After etching silica, controlled mesopores with sizes ranging from 3 to 10 nm were generated and microporosity was inherited as well in the mesoporous PAF-45HX materials.