Investigation of MOVPE growth of silicon δ‐doped GaAs, AlAs and AlxGa1‐xAs epilayers and different methods used for their characterisation are presented. The epitaxial structures were grown in an atmospheric pressure horizontal AIX 200 Aixtron reactor. Delta doping was formed by SiH4 introduction during the growth interruption. The influence of the growth temperature and AlxGa1‐xAs composition on δ‐doping characteristics, carrier concentration and mobility is discussed. Properties of the investigated Si d‐doped structures were examined using capacitance‐voltage measurements, Van der Pauw‐Hall measurements (300K, 77K), photocurrent measurements, photoreflectance spectros‐copy and X‐ray measurements.