The exploration of Pickering emulsions is very significant owing to their versatile and important applications in many scopes. In this study, synthesis of a novel kind of single-chain polymer nanoparticle (SCPN) and its stabilized Pickering emulsions were demonstrated. To this end, linear-dendritic diblock copolymers consisting of poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA) blocks and four-generation dendritic aliphatic polyester blocks (G(4)) have been first synthesized by the combination of click chemistry and reversible addition-fragmentation chain transfer (RAFT) polymerization reaction. The subsequent intramolecular cross-linking of the PDMAEMA block of PDMAEMA-b-G(4) copolymers in DMF using 1,4-diiodobutane as cross-linkers afforded Janus-like SCPNs that exhibited a cross-linked PDMAEMA head tethered by a short dendritic tail. The molecular weight and distribution together with the structure of polymers were carefully characterized by GPC and NMR spectroscopy. By the employment of the as-synthesized Janus-like SCPNs as Pickering emulsifiers, aqueous and nonaqueous Pickering emulsions including water-in-oil and oil-in-oil as well as ionic liquid-in-oil were generated. Under the same conditions, it was found that the long-term stabilities of Pickering emulsions stabilized by Janus-like SCPNs were superior to those of Pickering emulsions stabilized by their linear quaternized PDMAEMA-b-G(4) by CH3I analogous.