The main objective of this research was to obtain calcium silicate units from alternative raw materials, such as the bottom ashes from the combustion of wooden boards (WBA), as a source of silica, and GeoSilex (G), a by-product with low energy and environmental costs generated in the manufacture of acetylene, as a source of lime. Once the raw materials were physically, mineralogically and chemically characterized, calcium silicate units were obtained by mixing different amounts of WBA residue (90-20 wt%) and G by-product (10-80 wt%). The mixtures were compressed at 10 MPa and cured in water for 28 days. The calcium silicate units were subjected to a wide experimental program that included the determination of physical properties (bulk density, apparent porosity and water absorption), mechanical properties (compressive strength), and thermal properties (thermal conductivity). Optimum values are obtained for calcium silicate units that contain a 1/1 WBA/G weight ratio, which have an optimal amount of SiO and CaO for the cementation reaction. The 50WBA-50g units have compressive strength values of 46.9 MPa and a thermal conductivity value of 0.40 W/mK. However, all calcium silicate units obtained comply with the European Standard EN 771-2: 2011 to be used as structural building materials.