β-Naphthol is an important synthon in organic synthesis and can participate in various chemical reactions due to its active chemical property at α-site, which has attracted a great attention from chemists. β-Naphthol can undergo various chemical transformations at α-position, such as alkylation, arylation, cyclization, amination, halogenation and so on, which can be used to construct structurally diverse naphthol derivatives with various biological activities. These naphthol derivatives can be used not only as the privileged skeletons of natural active drugs, but also as the building blocks for the preparation of the important intermediates in chemical synthesis. In recent years, chemical reactions based on β-naphthol at α-site have emerged one after another. The reactions of β-naphthol at α-position are reviewed from the aspects of C-