The direct bonding of Si wafers reproducibly forms dislocation networks (DN) with a microscopic structure defined by the mutual crystallographic orientation between the pair of wafers used for the bonding procedure. This allows studying the electrical and optical properties of specific dislocations. In the present work three different DN structures were investigated using transmission electron microscopy (TEM), photoluminescence (PL) and deep level transient spectroscopy (DLTS). The results show close correlation between the structural, electrical and optical properties of dislocations and opens a possibility to identify structural peculiarities of the dislocations responsible for the high intensity of photoluminescence. Namely, the obtained results suggest that PL at ∼0.8 eV is related to screw dislocations in DN. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)