Two series of benzoxazines are synthesized from a set of isomeric monofluorophenols (o-, m-, and p-fluorophenols), two polyetheramines (Jeffamine D230 and D400), and formaldehyde. The chemical structures of the benzoxazines are confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy. For m-fluorophenol-based benzoxazines, the two sets of data appeared in the C-13, DEPT-135, and F-19 NMR spectra indicate that each product obtained is a mixture of two isomers. The ring-opening polymerization temperatures for ortho, meta, and para isomers in the two series of benzoxazines are in descending order para > ortho > meta. The glass transition temperatures (T(g)s) of the resultant polybenzoxazines are in ascending order ortho < para < meta. The polybenzoxazines exhibit thermally induced one-way dual-shape memory effect based on T-g, and the shape memory performance are excellent in tensile, bending, and twisting tests. Under motion constraints in a tensile deformation mode, the D400-based polybenzoxazines show higher shape recovery ratios compared with the corresponding D230 counterparts.