The electrical and optical properties of wafer bonded unipolar silicon‐silicon junctions were investigated. The interfaces, bothn‐ntype andp‐ptype, were prepared using wafers with hydrophilic surfaces. The current versus voltage characteristics, the current transients following stepwise changes in the applied bias, and the capacitance versus voltage characteristics as well as the temperature dependence of the current and capacitance were experimentally obtained and theoretically modeled. The proposed model assumes two distributions of interface states, one of acceptors and one of donors, causing a potential barrier at the bonded interface. It is argued that the origins of the interface states are impurities and crystallographic defects in the interfacial region. The capacitance of the bonded structures includes contributions from the depletion regions as well as from minority carriers. When bondedn‐ntype samples were illuminated with light of photon energies larger than the silicon band gap the current across the junction increased. This is caused by the photogenerated increase in the minority carrier concentration in the interfacial region, which results in a lowering of the potential barrier. Illumination ofn‐ntype structures with light of photon energies lower than the band gap caused a considerable photocurrent at low temperatures. In this case the observed behavior cannot be explained by interaction with the interface states. Instead, the mechanism is the change in the occupancy of deep electron traps caused by the illumination. These traps are located in the silicon in a small volume around the bonded interface with energies close to the center of the band gap and with a peak concentration of about 1013cm−3. Impurities present on the silicon surfaces before bonding and impurities gettered to the bonded interface are possible reasons for the increased concentration of deep electron traps in the vicinity of the bonded interface.