We synthesized Ca-containing FSM-16 (Ca-FSM-16) for use as a solid base catalyst for the Knoevenagel condensation reaction. Extended X-ray absorption fine structure (EXAFS) results indicated that Ca species were introduced as a calcium silicate-like phase with distorted tetrahedral coordination into the pore walls of FSM-16. Compared with conventional aminopropyl-functionalized mesoporous silica, Ca-FSM-16 showed higher activity as a solid-base catalyst for the Knoevenagel condensation reaction.