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This invention belongs to the field of organic optoelectronic technology, and discloses a class of polymer photoactive materials containing thermally desorbable functional groups and flexible segments, as well as their preparation and application. The structure of the polymer photoactive material containing thermally desorbable functional groups and flexible segments is shown in Formula I below. In Formula I, at least one unit among the D unit, A unit, and flexible segment contains a thermally desorbable group, and the number of thermally desorbable groups on each unit containing the thermally desorbable group is 1 to 4, relatively independently. These polymers have good solubility and can be processed into smooth films through solution processing. Furthermore, at the thermal desorption annealing temperature (T... a Additional heat treatment of the resulting film leads to the removal of thermally desorbed groups, thereby eliminating its strong solubility in organic solvents and making it a solvent-resistant layer that will not be corroded by the solution processing of the remaining layers, thus providing a guarantee for subsequent lamination processing.