Pure GaAs and GaAs1− xBix alloys with different Bi ratios (1%, 2.5%, 3.5%) fitted with silver contacts were measured with a dielectric spectroscopy device. Dielectric characterization was performed at room temperature in the frequency range of 0.1 Hz to 1 MHz. GaAs exhibits three relaxation regions corresponding to space-charge, dipolar and ionic polarizations in sequence with increasing frequency while GaAs1− xBix samples show only a broad dipolar polarization in the same frequency range. This result proves the filling of the lattice with Bi through making a new bonding reducing the influence of ionic polarization. This finding supports the previous results concerning optical properties of GaAs1− xBix, presented in the literature.