Efficiency improvement is important for new transport layer protocols. Stream Control Transmission Protocol (SCTP), proposed by IETF, is to improve the efficiency and security of the transport layer. SCTP is featured by Multi-homing and Multi-streaming. Though the source and destination nodes exchange the available address list after four-way handshake in the initial stage, the quality of each available link is unknown. Hence, the chosen primary path may not be the best path which implies inefficiency. In this paper, we propose a scheme to add two new Chunks which carry the status of each alternative path during the four-way handshake of SCTP. Hence, the path of the best quality will be selected as the primary path. The simulation, by NS2, results show when the best path is selected to transmit data, the throughput could be improved up to 83.3% as compared with the worst case.