First hierarchical titanium phosphate (TiPO) materials with Multiple porosities of different lengths (meso-macroporous and meso-macro-macroporous) were synthesized by the self-formation process. The further tuning of the porous hierarchy by using the poly(ethylene oxide) surfactant technique was demonstrated. The macroporous structure (50160 nm in size) of TiPO with mesoporous walls could be self-formed in the absence of any templatable agents, including surfactant molecules. On the basis of spontaneous structurization, the addition of a small quantity of nonionic poly(ethylene oxide) surfactant (e.g., 5%) led to an improvement in macroporosity in abundance and in regularity with a slight enlargement in macropore sizes to 80-250 nm. Interestingly, a secondary, larger macropore system with parallel channels 500-1000 nm in size was generated when the synthesis was performed with moderately increasing the content of surfactant (10%), giving rise to an unprecedented trimodal meso-macro-macroporous structure. A uniform three-dimensional co-continuous macroporous structure with accessible wormhole-like mesoporous walls was synthesized by using the higher content of surfactants. This is a direct demonstration of tailoring the porous hierarchy of different lengths integrated in one solid body by fine-tuning the self-formation process and the participation Of surfactant. The synthesized hierarchical titanium phosphates possess interesting optical and acidic properties, which should be significant for large application potential from catalysis and separation to electrochromic devices, fuel cells, and bioactive materials.