The mix proportioning of extrusion-based 3D-printed cementitious material should balance printability and hardened properties. This paper investigated the effects of three key mix proportion parameters of 3D-printed alkali-activated fly ash/slag (3D-AAFS) mortar, i.e., the sand to binder (s/b) ratio, fly ash/ground granulated blast-furnace slag (FA/GGBS) ratio, and silicate modulus (Ms) of the activator, on extrudability, buildability, interlayer strength, and drying shrinkage. The results showed that the loss of extrudability and the development of buildability were accelerated by increasing the s/b ratio, decreasing the FA/GGBS ratio, or using a lower Ms activator. A rise in the s/b ratio improved the interlayer strength and reduces the drying shrinkage. Although increasing the FA/GGBS mass ratio from 1 to 3 led to a reduction of 35% in the interlayer bond strength, it decreased the shrinkage strain by half. A larger silicate modulus was beneficial to the interlayer bond strength, but it made shrinkage more serious. Moreover, a simple centroid design method was developed for optimizing the mix proportion of 3D-AAFS mortar to simultaneously meet the requirements of printability and hardened properties.