3D-particulate and 1D-fiber structures of multiferroic bismuth ferrite (BiFeO₃/BFO) and their composites with 2D-graphene oxide (GO) have been developed to exploit the different scheme of interfacial engineering as 3D/2D and 1D/2D systems. Particulates and fibers of BFO were developed via sol-gel and electrospinning fabrication approaches respectively and their integration with GO was performed via the ultrasonic-assisted chemical reduction process. The crystalline and phase formation of BiFeO₃ and GO was confirmed from the XRD patterns obtained. The electron microscopic images revealed the characteristic integration of 3D particulates (with average size of 100 nm) and 1D fibers (with diameter of ~150 nm and few μm length) onto the 2D GO layers (thickness of ~27 nm). XPS analysis revealed that the BFO nanostructures have been integrated onto the GO through chemisorptions process, where it indicated that the ultrasonic process engineers the interface through the chemical modification of the surface of these 3D/2D and 1D/2D nanostructures. The photophysical studies such as the impedance and photocurrent measurements showed that the charge separation and recombination resistance is significantly enhanced in the system, which can directly be attributed to the effective interfacial engineering in the developed hetero-morphological composites. The degradation studies against a model pollutant Rhodamine B revealed that the developed nanocomposites exhibit superior photocatalytic activity via the effective generation of OH radicals as confirmed by the radical analysis studies (100% degradation in 150 and 90 min for 15% GO/BFO particulate and fiber composites, respectively). The developed system also demonstrated excellent photocatalytic recyclability, indicated their enhanced stability.