In reconfigurable intelligent surface (RIS)-assisted symbiotic radio (SR), the RIS acts as a secondary transmitter by modulating its information bits over the incident primary signal and simultaneously assists the primary transmission, then a cooperative receiver is used to jointly decode the primary and secondary signals. Most existing works of SR focus on using RIS to enhance the reflecting link while ignoring the ambiguity problem for the joint detection caused by the multiplication relationship of the primary and secondary signals. Particularly, in case of a blocked direct link, joint detection will suffer from severe performance loss due to the ambiguity, when using the conventional on-off keying and binary phase shift keying modulation schemes for RIS. To address this issue, we propose a novel modulation scheme for RIS-assisted SR that divides the phase-shift matrix into two components: the symbol-invariant and symbol-varying components, which are used to assist the primary transmission and carry the secondary signal, respectively. To design these two components, we focus on the detection of the composite signal formed by the primary and secondary signals, through which a problem of minimizing the bit error rate (BER) of the composite signal is formulated to improve both the BER performance of the primary and secondary ones. By solving the problem, we derive the closed-form solution of the optimal symbol-invariant and symbol-varying components, which is related to the channel strength ratio of the direct link to the reflecting link. Moreover, theoretical BER performance is analyzed. Finally, simulation results show the superiority of the proposed modulation scheme over its conventional counterpart.