Understanding the complexity of the chemical and microstructural evolution of cement during hydration remains a controversial subject, and although numerous techniques have been used to assess this process, further insight is still needed. Alternating current impedance spectroscopy has been demonstrated to be a sensitive and powerful technique for cement characterisation in both fresh and hardened states; however, it has also shown certain experimental limitations (e.g. data interpretation, electrode, and parasitic effects) that prevent its wider acceptance. This study assesses electrochemical cell design and the impedance response during cement hydration. The results show that a significant decrease in the parasitic effects at high frequencies (caused mainly by leads and electrode effects) can be achieved through an optimal cell design and impedance measurements correction, enabling correlation of impedance measurements to particular aspects of the cement hydration process. However, due the limited solid phase microstructural development and the high conductivity of cement paste at low degrees of hydration, the parasitic effects could not be fully eliminated for fresh or early-age cement pastes.