This study focuses on the relationship between the complexity of pore structure and capillary water absorption of concrete, as well as the connection behavior of concrete in specific directions. In this paper, the water absorption of concrete with different binders was tested during the curing process, and the pore structure of concrete was investigated by mercury intrusion porosimetry (MIP). The results show that the water absorption of concrete with mineral admixtures is lower, mainly due to the existence of reasonable pore structure. The effect of slag on concrete modification is more remarkable comparing with fly ash. In addition, the analysis shows that the pore with different diameters has different fractal characteristics. The connectivity probability and water absorption of unidirectional chaotic pore are linearly correlated with the pore diameter of 50–550 nm, and the correlation coefficient reaches a very significant level, and detailed analysis was undertaken to interpret these results based on fractal theory.