This paper conducts a detailed study on the thermal transport and thermoelectric properties of Li2Rb(Cs)Bi and analyzes the optical phonon frequency shift caused by considering anharmonicity. We mainly focus on studying the microscopic mechanism of the difference in lattice thermal conductivity (κL) of the two materials. By calculating the group velocity, scattering rate, scattering phase space and scattering sub-process, it is concluded that κL is mainly dominated by the acoustic branch. Due to its small group velocity and large scattering rate, Li2CsBi has a low κL, which is 0.60 W m−1K−1 at 300 K. Research results show that n-type Li2CsBi has a higher ZT value of about 2.1 at T = 900 K, while p-type Li2RbBi has a higher ZT value of about 1.5 at the same temperature. These results provide an important theoretical basis for the application of Li2Rb(Cs)Bi in the field of thermoelectric conversion.