Hierarchically porous metal-organic frameworks (HP-MOFs) have attracted a lot of attention in recent years because their hierarchical pores have critical importance in strengthening their performance, including guest diffusion kinetics, catalytic activity, and selectivity, especially with reference to large molecules. However, the preparation method for simple, controllable, and stable HP-MOFs at a micro-/meso-/macroscopic scale is still lacking. Herein, we showed several forms of HKUST-1 (HKUST = Hong Kong University of Science and Technology) by simply changing the copper source and solvent type, including original micron HKUST-1 (O-HKUST-1), half-foam HKUST-1 (HF-HKUST-1), and fully foam HKUST-1 (F-HKUST-1). Compared to O-HKUST-1, HF-HKUST-1 and F-HKUST-1 possessed an apparent hierarchically porous structure due to the high fusion of HKUST-1 nanocrystals. Especially in F-HKUST-1, all of the HKUST-1 nanocrystals were tightly integrated into each other, which formed a holistic hollow foam structure. Hence, F-HKUST-1 exhibited the highest adsorption capacity toward large molecules, including proteases, phosphotungstic acid, and organic dyes. Meanwhile, F-HKUST-1 presented the highest photocatalytic degradation capability for rhodamine B. Furthermore, F-HKUST-1, loaded with phosphotungstic acid (F-HKUST-1@PTA), which was used as a catalyst, indicated a catalytic capacity comparable to that of a homogeneous catalyst (pure phosphotungstic acid).