For a semiconductor material, the characterization of its electronic band structure is very important for analyzing its physical properties and applications in semiconductor-based devices. Photoreflectance spectroscopy is a contactless and highly sensitive method of characterizing electronic band structures of semiconductor materials. In the photoreflectance spectroscopy, the modulation of pumping laser can cause a change in material dielectric function particularly around the singularity points of joint density of states. Thus the information about the critical points in electronic band structure can be obtained by measuring these subtle changes. However, in the conventional single-modulated photoreflectance spectroscopy, Rayleigh scattering and inevitable photoluminescence signals originating from the pumping laser strongly disturb the line shape fitting of photoreflectance signal and influence the determination of critical point numbers. Thus, experimental technique of photoreflectance spectroscopy needs further optimizing. In this work, we make some improvements on the basis of traditional measurement technique of photoreflectance spectroscopy. We set an additional optical chopper for the pumping laser which can modulate the amplitude of the photoreflectance signal. We use a dual-channel lock-in amplifier to demodulate both the unmodulated reflectance signals and the subtle changes in modulated reflectance signals at the same time, which avoids the systematic errors derived from multiple measurements compared with the single-modulated photoreflectance measurement. The combination of dual-modulated technique and dual-channel lock-in amplifier can successfully eliminate the disturbances from Rayleigh scattering and photoluminescence, thus improving the signal-to-noise ratio of the system. Under a visible laser (2.33 eV) pumping, we measure the room-temperature dual-modulated photoreflectance spectrum of semi-insulating GaAs in a region from near-infrared to ultraviolet (1.1 ～6.0 eV) and obtain several optical features which correspond to certain critical points in its electronic band structure. Besides the unambiguously resolved energy level transition of E0 and E0+0 around the bandgap, we also obtain several high-energy optical features above the energy of pumping laser which are related to high-energy level transitions of E1, E1+1, E0' and E2 in the electronic band structure of GaAs. This is consistent with the results from ellipsometric spectroscopy and electroreflectance spectroscopy. The results demonstrate that for those high-energy optical features, the mechanism for photoreflectance is that the photon-generated carriers modulate the build-in electric field which affects the overall electronic band structures, rather than the band filling effect around those critical points. This indicates that dual-modulated photoreflectance performs better in the characterization of semiconductors electronic band structure at critical point around and above its bandgap.