The present invention relates to a rapid assembled small-sized block polymer material with low quenching temperature and the preparation and application thereof. In particular, the present invention discloses a block copolymer, and glass transition temperature of the block copolymer is less than 120° C. The present invention also discloses the preparation and application of the block copolymer. The block copolymer can achieve excellent phase separation and rapid patterning at a lower annealing temperature (e.g. 80° C.) and a shorter annealing time (e.g. 30 s), and a photolithographic pattern with a very high resolution (e.g. 5 nm half-pitch) can be further obtained by etching, which provides a new photolithographic mean for further extension of Moore's Law to achieve semiconductor photolithography with a resolution of less than 10 nm, or even 5 nm (half-pitch).