The packing form of atoms or molecules in the structure and elemental spatial distribution are the core problems of condensed matter. Precise revelation of local structure is one of the most important methods to address such kind of issues. The acquisition of local structural information, which is directly correlated to chemical bonding, provides the deep insight of chemical reaction and understanding for the intrinsic structure-function relationship of design for functional materials. The atomic pair distribution function(PDF) based on the total scattering method, considering the spatial distribution regularities of atomic pair distance in radial direction, demonstrates the full-range structural information of condensed matter systems with different crystallinity and agglomeration. This review starts from the theoretical basis of total scattering and PDF. Refer to the differences of aggregation morphology and structural chemistry features, the representative examples with local structural novelty are shown. The specific introduction for the recent results about structural evolution demonstrate the distinct characteristics from short to long range during the application of the atomic pair distribution function combining in-situ temperature field and reverse monte carlo method. The new viewpoint from the local structure to the chemical reaction, optimization of functional properties and responses to external fields is proposed.