Optical code-division multiple-access (CDMA) techniques provide multi-user data transmission services in optical wireless and fiber communication systems. Several signature codes, such as modified prime sequence codes (MPSCs), generalized MPSCs (GMPSCs) and modified pseudo-orthogonal M-sequence sets, have been proposed for synchronous optical CDMA systems. In this paper, a new scheme is proposed for synchronous optical CDMA to increase the number of users and, consequently, to increase the total data rate without increasing the chip rate. The proposed scheme employs a GMPSC and an extended bi-orthogonal code which is a unipolar code generated from a bipolar Walsh code. Comprehensive comparisons between the proposed scheme and several conventional schemes are shown. Moreover, bit error rate performance and energy efficiency of the proposed scheme are evaluated comparing with those of the conventional optical CDMA schemes under atmospheric propagation environment.