The precise synthesis of multifunctional poly(ionic liquid)s (MFPILs) featuring basic sites, mesoporous channels, and hydrophobicity continues to be a substantial challenge. Moreover, the directional conversion of lignite to monocyclic arenes (MCAs) is highly attractive but particularly challenging on account of its geometrical complexity and chemical inertness. The efficiency of lignite directional conversion to MCAs over solid bases is substantially decreased by the presence of water molecules leading to the deactivation and leaching of basic sites. Herein, the novel solid bases, i.e., MFPILs with dibasic sites, unique hydrophobicity, and abundant mesoporous channels, were successfully fabricated by a radical multicomponent cross-linked copolymerization for the first time. Even more excitedly, the resulting MFPILs were demonstrated to be very efficient for directional catalytic hydroconversion of extraction residue from Dahuangshan lignite (DLER) into MCAs with 32.3 wt% yield, which is by far the highest value reported for lignite-derived MCAs by solid bases under similar conditions. The synergistic catalysis, i.e., hydrophobic microenvironment, mesoporous confinement, and synergistic effect of dibasic sites, for active hydrogen transfer of DLER conversion into MCAs over MFPILs is confirmed by characterization methods. The work not merely sheds substantial light on developing the novel solid bases, but also exhibits a potentially powerful catalyzing strategy to synthesize MCAs.