The KBiFe2O5 (KBFO) compound was synthesized by using a conventional solid-state reaction method and its structural, optical, electrical, and magnetic properties were thoroughly gone through. It was found that KBFO possessed a monoclinic structure with P2/c space group and could be prepared within the calcination temperature range from 1023 K to 1073 K. No structural transformation was approved from room temperature to the decomposition temperature for KBFO. A broad absorption band at the range 300–650 nm and the optical band gap of about 1.76 eV were approved. Dielectric property measurements revealed a Maxwell-Wagner type dielectric dispersion for KBFO and approved the magnetoelectric effect. An evident photoelectric response with the VOC and Isc of around −0.5 V and 20 nA was obtained. It was presented that at low temperatures a weak ferromagnetism was verified by the ferromagnetic hysteresis loop due to the canting of the magnetic moments of G-type antiferromagnetic order in KBFO. In summary, the multiferroicity in KBFO were approved experimentally and could be regarded as a potential candidate for the ferroelectric photovoltaic applications.