We have synthesized doubly thermosensitive core-shell microspheres composed of chemically cross-linked poly(N-n-propyl acrylamide-co-styrene) (P(nPA-co-S)) with different styrene contents as the core and linear poly(N,N-diethyl acrylamide) (PDEA), poly(N-isopropyl acrylamide) (PiPA), or poly(N-isopropyl methacrylamide) (PiPMA) as the shells. The morphologies and swelling properties of the core and the core-shell microspheres have been studied. The P(nPA-co-S) copolymers have a similar volume phase transition temperature regardless of the styrene content, indicating a two-layer structure in the microspheres with a PS-rich inner core and a PnPA-rich outer layer resulting from soap-free emulsion polymerization in water. Upon the addition of the second shell composed of linear thermosensitive polymers, the core-shell microspheres display a two-step shrinking behavior when heated. The P(nPA-co-S) core exhibits a volume phase transition temperature at 13-15 degrees C, while the shells of PDEA, PiPA, and PiPMA have volume phase transition temperatures at 28, 32, and 42 degrees C, respectively. The core-shell microspheres are composed of three layers and possess two volume phase transition temperatures.