Disclosed is a method and system for mutually exchanging capability information of UEs for communication between a Circuit-Switched (CS) and IMS services (CSI) UE, which can use a CS call for voice communication while using an IMS session for PS service, and an IMS UE which uses an IMS session for both voice communication and PS service. A MGCF performs interworking of capability information between a CS message and an IMS message so that the IMS UE can process UE capability information through an IMS session request/response. When a call request message containing no capability information is created from a UE not supporting capability exchange, a CSI AS transfers the call request message to a peer UE after inserting estimable capability information of the UE into the call request message, and stores capability information of the counterpart UE for the UE.