The thermochromic mechanism and the structure-property regulation principle of reversible thermochromic polydiacetylene (PDA) materials have always been a challenging issue. In this work, a series of diacetylene monomers (m-PCDA) containing phenyl and amide or carboxyl groups were synthesized from 10,12-pentacosadiynoic acid (PCDA) through the esterification or amidation reactions. The effects of the number and the distribution of the functional groups in m-PCDA molecules on their solid-state polymerization capability, and the thermochromic mechanism of their corresponding polymers (m-PDA) were investigated and discussed in detail. The results show that the m-PCDA monomers containing both benzene ring and groups that can form hydrogen bonding interactions have strong intermolecular interaction, and are easy to carry out the solid phase polymerization under 254-nm UV irradiation to obtain the corresponding new thermochromic m-PDA materials. The thermochromic behavior of m-PDA depends on its melting process. The initial color-change temperature (blue to red) is determined by the onset melting temperature, and the temperature range in which reversible color recovery can be achieved by repeat heating-cooling treatment is determined by its melting range. According to the proposed thermochromic mechanism of PDA, various new PDA materials with precise thermochromic temperatures and reversible thermochromic temperature ranges can be designed and synthesized through the appropriate introduction of benzene ring and groups that can form hydrogen bonding interactions into the molecular structure of linear diacetylene monomer. This work provides a perspective to the precise molecular structure design and the property regulation of the reversible thermochromic PDA materials.