An effective method to improve the photocatalytic per-formances of powder catalysts is to use the intal electric field from ferroelectrics to separate photogenerated charge carriers. The design and engineering of a complex hetero-junction with a hierarchical pore structure is highly desirable for the efficient application of ferroelectric materials in photocatalysis. Here, we present a novel strategy using two templates to fabricate PbTiO3/TiO2/carbon (PTC) nanocomposites with a tunable microstructure. A hard SiO2 template combined with an ice template followed by an appropriate pyrolysis procedure introduced tri-modal (micro-, meso-, macro-) porosity. The as-prepared PTC nanocom-posites with optimal mass ratio exhibited excellent photocatalytic and photoelectrochemical performances. PbTiO3/TiO2 annealed at 900 ℃ (PTC-900) showed a MB degradation rate of 0.21 and 0.021 min?1 under UV and visible light irradiation, which are, respectively, 7.2 and 3 times those of pure PbTiO3. The photocurrent density of the compos-ite catalyst is 1.48 mA cm?2 at the potential of 1.0 V versus saturated calomel electrode, and the rates of hydrogen generation of PTC-900 are as high as 2360 and 9.6 μmol h?1 g?1 under UV and visible light irradia-tion, respectively. More importantly, the simultaneous application of ultrasound-induced mechanical waves further improved the photocata-lytic reactivity. This work serves to improve understanding on the design of ferroelectric/piezoelectric photocatalysts with a hierarchical pore structure and also proposes a widely applicable strategy for the fabrication of high-performance micro–nano/nano–nano structures.