The high environmental impact associated with ordinary Portland cement production has driven increasing interest in alternative low-carbon binder systems based on alkali-activated materials. In this context, geopolymers synthesized from metakaolin and supplemented with natural or industrial by-products represent a promising route toward more sustainable construction materials. In this study, the partial substitution of metakaolin (MK) with stainless steel slag (SSS, calcium rich) or volcanic ash (VA, silica-rich) in alkali-activated cements (AACs) synthesis was investigated by analyzing their physical, mechanical, and thermal properties. The structural evolution associated with alkali activation was assessed using X-ray diffraction (XRD) and ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR). Fourier transform infrared spectroscopy (FTIR) revealed a shift in the main Si–O–T (T = Si, Al) asymmetric stretching band toward lower wavenumbers (≈1000 cm⁻¹), indicating changes in the aluminosilicate network consistent with geopolymer formation. Scanning electron microscopy (SEM) was used to examine the microstructural features of the hardened matrices. The results showed that samples containing 50 wt.% MK and 50 wt.% VA achieved the highest mechanical performance, with compressive and flexural strengths of 46.29 MPa and 16.2 MPa at 7 days, increasing to 56.66 MPa and 17.58 MPa at 28 days of curing, respectively. In contrast, the samples containing 50 wt.% MK and 50 wt.% SSS displayed lower strength development, reaching compressive and flexural strengths of 27.7 MPa and 9.6 MPa at 7 days and 41.01 MPa and 13.68 MPa at 28 days. Additionally, thermal conductivity decreased with increasing porosity and decreasing bulk density, highlighting the potential of these AACs as structurally efficient materials with improved thermal insulation performance.