The invention belongs to the field of high molecular materials, and specifically relates to a carbon-dioxide-based polycarbonate material with optical activity as well as a preparation method and application thereof. The content of carbonate in a polymer chain is 90-100%, and the identical structure of a polymer ranges from 90.0% to 99.9%. The enantio-selectivity of diol measured ranges from 90.0% to 99.9% after the polymer is hydrolyzed by aqueous liquor of sodium hydroxide. The molecular weight of the polymer is adjustable in a range from 103 to 106. The molecular weight distribution is less than 2.0 and the tacticity is 90-100%. The polymer is simply heated to obtain crystalline polycarbonate. The polycarbonate material provided by the invention has the advantages of easiness in crystallization, high transparency and the like. The polymer can be further used for synthesizing hydroxyl carbonate with optical activity and polyhydric alcohols with two chiral carbon centers, wherein the enantiomeric excess ranges from 90.0% to 99.9%, thereby providing wide prospect to industrial application of the polycarbonate material.