The topotactic polymerization reaction is a special case of more general topochemical reactions, and it is defined as the photoinduced solid-state polymerization reaction, in which the space group symmetry is kept unchanged between the initial monomer and the final polymer crystals and the morphology or crystal shape is also mostly unchanged through this solid-state polymerization reaction. The experimental check of the topotactic reaction is made by analyzing the structure relation between the original monomer single crystal and the resultant polymer single crystal. A half century ago, the 2,5-distyrylpyrazine (DSP) monomer single crystal was discovered as the first example of the [2 + 2]-type cycloaddition topotactic polymerization reaction. However, while the crystal structure of DSP monomer single crystal was analyzed, the crystal structure analysis of the corresponding polymer species had been left pending over these several tens of years, although the unit cell parameters and space group were report...