Due to the potential applications for spintronics devices, diluted ferromagnetic semiconductors (DMS) have received extensive attention for decades. However, in classical Ⅲ–Ⅴ based DMS material, such as (Ga,Mn)As, heterovalent (Ga ³⁺, Mn ²⁺) doping results in lack of individual control of carrier and spin doping, and seriously limited chemical solubility. The two difficulties prevent furtherincrease of the Curie temperature of the Ⅲ–Ⅴ based DMS. To overcome these difficulties, a series of new types of DMS with independent spin and charge doping have been synthesized, such as Ⅰ–Ⅱ–Ⅴ based LiZnAs and Ⅱ–Ⅱ–Ⅴ based (Ba,K)(Zn,Mn) ₂As ₂. In these new materials, isovalent (Zn,Mn) substitution is only spin doping, while charge is independently doped by heterovalentsubstitution of non-magnetic elements. As a result (Ba,K)(Zn,Mn) ₂As ₂obtains the reliable record of Curie temperature (230 K) among DMS in which ferromagnetic ordering is mediated by itinerate carriers. In this review, we summarize the recent development of the new DMS materials with following aspects: 1) the discovery and synthesis of several typical new DMS materials; 2) physical properties studies with muon spin relaxation and in-situ high pressure techniques; 3) single crystal growth, Andreev reflection junction based on single crystal and measurements of spin polarization.