The invention provides a preparation method of dodecafluoroheptyl-propyl polyhedral oligomeric silsesquioxane, which comprises the following steps: dripping each 1mol of dodecafluoroheptyl-propyl-trimethoxylsilane into 250-10000ml of organic solvent under the condition of 0-40 DEG C, carrying out hydrolysis condensation reaction under the action of acid catalysis, carrying out the reaction for a certain period of time, and carrying out concentration, filtration, drying and other steps for preparing dodecafluoroheptyl-propyl polyhedral oligomeric silsesquioxane (dodecafluoroheptyl-propyl POSS) crystals. The invention further provides the dodecafluoroheptyl-propyl polyhedral oligomeric silsesquioxane. The method has simple and easy process, low cost, high yield and high product purity, and the prepared dodecafluoroheptyl-propyl polyhedral oligomeric silsesquioxane product has excellent hydro-oleophobic performances, heat resistance, flame retardance and low dielectric constant performance, and can be widely applied in the fields of polymer modification, hydro-oleophobic interface materials, flame retardants, low dielectric constant materials, building coatings, space materials, medical materials, light-emitting materials, liquid crystal materials and the like.