Silica sulfuric acid (SSA) mediated synthesis of naphtho[2,1‐b]furan derivatives starting from β‐nitrostyrene derivatives and β‐naphthol derivatives under solvent‐free conditions have been developed. The scope of SSA as a heterogeneous catalyst is extended to one‐pot multicomponent reaction for the synthesis of functionalized pyrazole derivatives under solvent‐free conditions from readily available β‐nitrostyrene derivatives, acetyl acetone, and hydrazine hydrate. The synthetic methods have significant advantages such as solvent‐free conditions, simple operation, shorter reaction times, ease and clean isolation procedures, and very good yields of products.