Understanding the relationship between the intrinsic characteristics of materials (such as rheological properties and structural build-up) and printability and controlling intrinsic characteristics of materials through additives to achieve excellent printability is vital in digital concrete additive manufacturing. This paper aims at studying the effects of material’s structural build-up on the interlayer bond strength of 3DPC with different time gaps. Structural build-up can indirectly affect the interlayer bond strength by affecting the surface moisture of concrete. Based on the structural build-up of 3DPC, a new parameter, maximum operational time (MOT), is proposed, which can be considered as the limit of time gap to ensure high interlayer bond strength. Slump-retaining polycarboxylate superplasticizer (TS) slightly slows down the physical flocculation rate, but increases the maximum operational time of the cement paste. Nano clay significantly increases the sort-term structural build-up rate and has the function of internal curing and water retaining. Composite with nano-clay and TS can reduce the loss of surface moisture of 3D printed layers, prevent the formation of interface weak layer, and increase the interlayer bond strength between printed layers. This contribution can provide new insight into the design of 3D-printed ink with good extrudability, outstanding buildability, and excellent interlayer bond strength.