Herein, we designed and synthesized a precursor with a three-fold node and successfully constructed covalent Sierpiński triangle (ST) fractals with boronic ester linkages both at the liquid/solid interface at room temperature and by thermal annealing in a water atmosphere under ambient conditions. Remarkably, large-scale ordered superstructures of covalent STs are constructed by thermal annealing, which paves the way for property investigation of STs.