Carbon nano tubes (CNT) has been introduced as an efficient nanomaterial in order to improve the mechanical and durability properties of concrete. The effect of CNT on the microstructures of cementitious materials has been widely reported. This paper combines a critical review on the effect of CNT on the pore and microstructure of cement composite with a discussion on the porosity measurement of pastes containing CNT using mercury intrusion porosimetry techniques (MIP). It was found that, surface treatment by H2S04 and HN03 solution forms carboxyl acid groups on CNTs, surfaces that lead to the improvement of reinforcement. In this scope, this review paper involves analyzing the effect of CNT on the microstructure and the pore structure of cementitious materials. The existing methods of measuring the porosity of cementitious material are reviewed, in particular, the contact angle measurement is discussed in detail in which the most effective parameters and possible errors of calculation is presented.