Ferroelectric barium titanate (BaTiO3) with an intrinsic spontaneous polarization performs multiple remarkable properties. Recently, ferroelectric BaTiO3 based materials and devices are fabricated in multi‐effects coupled systems, such as self‐powered ultrasensitive sensing, energy harvesting, and electrochemical applications, which have gained growing interest with worldwide increasing researches. This review places a focus on current achievements in ferroelectric BaTiO3 based multi‐effects coupled materials and devices for capacitors, nanogenerators, sensors, electrochemistry, and other applications. First, the structure–activity relationship of BaTiO3 materials including various crystal structures and different morphologies is reported. It is interesting that multi‐effects coupled electronic devices and systems combining multiple properties have attached significant effort to realize enhanced performance contrasted to device applications with single effect. Finally, a brief understanding of opportunities and challenges for ferroelectric BaTiO3 based multi‐effects coupled materials and devices is given. The intention of this review is to encourage more effort in this nontoxic intelligent material, and impel more attention in pushing progress of this field in the future.