The rapid increase in additive manufacturing applications in all industries has highlighted the lack of innovative technologies and processes in the construction industry. Several European and international policies are in place to guide the development of the technological processes involved in the construction industry toward a sustainable future. Considering the global concerns regarding this industry, the purpose of this study was to develop new cement-based materials that are capable of accelerated hydration and early strength development for use in additive manufacturing. Ca(NO3)2·4H2O, Al2(SO4)3·18H2O and Na2S2O3·5H2O were used to obtain the accelerating effect in the hydration of Portland cement. Based on results obtained from X-ray diffraction (XRD), scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM/EDX) techniques, as well as low-field nuclear magnetic resonance relaxometry (LF-NMR) techniques, it was demonstrated that all accelerators used have a quickening effect on cement hydration. The addition of Na2S2O3·5H2O or combined Na2S2O3·5H2O and Ca(NO3)2·4H2O led to obtaining new cement-based materials with early strength development and fast hydration of microorganized internal structures, critical characteristics for 3D printing.