New piezoelectric and triboelectric materials for energy harvesting are being widely researched to reduce their processing cost and complexity and to improve their energy conversion efficiency. In this study, BaTiO3 films of various thickness were deposited on Ni foams by R.F. magnetron sputtering to study the piezoelectric and triboelectric properties of the porous spongy structure materials. Then piezoelectric nanogenerators (PENGs) were prepared with spongy structured BaTiO3 and PDMS composite. The output performance exhibited a positive dependence on the thickness of the BaTiO3 film, pushing load, and poling. The PENG output voltage and current were 4.4 V and 0.453 μA at an applied stress of 120 N when poled with a 300 kV/cm electric field. The electrical properties of the fabricated PENG were stable even after 5,000 cycles of durability testing. The triboelectric nanogenerators (TENGs) were fabricated using spongy structured BaTiO3 and various polymer films as dielectrics and operated in a vertical contact separation mode. The maximum peak to peak voltage and current of the composite film-based triboelectric nanogenerator were 63.2 V and 6 μA, respectively. This study offers new insights into the design and fabrication of high output nanogenerators using spongy structured materials.