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Dibenzylidene sorbitol (DBS) is a sugar derivative that is capable of self-organizing into a 3D nanofibrillar network at relatively low concentrations in a wide variety of organic solvents and polymer melts. This research was aimed at determining the effect of DBS on vinyl conversion, polymerization shrinkage, and mechanical strength of bioactive dental composites containing zirconyl-modified amorphous calcium phosphate (Zr ACP) and a polymer matrix derived from the photopolymerization of ethoxylated bisphenol-A dimethacrylate (EBPADMA). Flexural strength was enhanced while polymerization shrinkage and its associated stress development were both significantly reduced by the incorporation of DBS into the composites.