The boundary parameters between contacting spherical bcc-Fe particles have been characterized with the Large Angle Convergent Beam Electron Diffraction (LACBED) technique. The average accuracy of measurements can reach 0.07°. The rotation parameters are interpreted using matrix algebra and evaluated according to the CSL model. The deviation between the experimental results and the reference misorientations given in the CSL model is determined. It is possible to reveal preferential misorientations between irregularly shaped particles with a size less than 100 nm. The method can be applied to nanoparticles and nanocrystalline materials with a wide range of grain orientations, and it is possible to modify it into an automatic method for TEM measurements.