We report on experimental observations of room temperature low frequency capacitance-voltage (CV) behaviour in metal oxide semiconductor (MOS) capacitors incorporating high dielectric constant (high-k) gate oxides, measured at ac signal frequencies (2 kHz to 1 MHz), where a low frequency response is not typically expected for Si or GaAs MOS devices. An analysis of the inversion regions of the CV characteristics as a function of area and ac signal frequency for both n and p doped Si and GaAs substrates indicates that the source of the low frequency CV response is an inversion of the semiconductor/high-k interface in the peripheral regions outside the area defined by the metal gate electrode, which is caused by charge in the high-k oxide and/or residual charge on the high-k oxide surface. This effect is reported for MOS capacitors incorporating either MgO or GdSiOx as the high-k layers on Si and also for Al2O3 layers on GaAs(111B). In the case of NiSi/MgO/Si structures, a low frequency CV response is observed on the p-type devices, but is absent in the n-type devices, consistent with positive charge (>8 x 10(10) cm(-2)) on the MgO oxide surface. In the case of the TiN/GdSiOx/Si structures, the peripheral inversion effect is observed for n-type devices, in this case confirmed by the absence of such effects on the p-type devices. Finally, for the case of Au/Ni/Al2O3/GaAs(111B) structures, a low-frequency CV response is observed for n-type devices only, indicating that negative charge (> 3 x 10(12) cm(-2)) on the surface or in the bulk of the oxide is responsible for the peripheral inversion effect. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4729331]