Exploitation of new polymerization with selectivity is of significance to the preparation of functional polymers and the study of their structure-property relationship. In this work, we successfully developed an efficient Ru(II)-catalyzed azide-alkyne click polymerization (RuAACP), of which the regioselectivity can be switched by the ligands on the Ru(II) catalysts. With RuH2(CO)(PPh3)(3) as catalyst, 1,4-regioregular polytriazoles (PTAs) with high weight-average molecular weights (M-w up to 15300) and high 1,4-regioregularities (the fraction of 1,4-isomer, F-1,F-4 up to 100%) were produced in satisfactory yields (up to 97.6%). In contrast, Cp*Ru(PPh3)(2)Cl-catalyzed AACP facilely yielded (up to 98.3%) 1,5-regioregular PTAs with high M-w (up to 15520) and F-1,F-5 (up to 100%). All the obtained PTAs exhibit good solubility and high thermal stability. The glass transition temperature (T-g) of 1,4-regioregular PTA is much higher than that of its 1,5-regioregular counterpart, revealing the considerable effect of the regiostructure on their T-g. Both 1,4- and 1,5-regioregular PTAs containing tetraphenylethene moieties in their backbones show aggregation-induced emission features. In addition, the impact of regiostructure on the light refractivity of the PTAs was also investigated, and 1,4-regioregular PTA possesses higher refractivity indices than 1,5-regioregular PTA.