In 2020, users in and around China had access to a new real-time precise point positioning (RTPPP) service with the BeiDou global navigation satellite system (BDS-3) B2b (PPP-B2b) signal. In this study, the quality of PPP-B2b products is first assessed and compared with the CNAV1 broadcast ephemeris. Then a mode of BDS-3 PPP time transfer with PPP-B2b (B2b-RTPPP) is developed and evaluated in static and kinematic modes. The results demonstrate that the discontinuity of orbit is improved by applying the PPP-B2b, and its root mean square errors (RMSEs) are 0.081 m, 0.165 m, and 0.107 m in the radial, along-track, and cross-track components, respectively. The standard deviation (STD) of the PPP-B2b clock offset is 0.08 ns, greatly better than that of the broadcast clock offset. For time transfer, the type A uncertainty of the B2b-RTPPP solution is approximately 0.1 ns in static mode, and approximately 0.3 ns in kinematic mode. The B1I/B3I B2b-RTPPP time transfer solution performs better than the B1C/B2a solution. For frequency stability, the modified Allan deviation (MDEV) of the B2b-RTPPP solution is comparable to that of the post-processing solution. The B1C/B2a combination has better short-term frequency stability than B1I/B3I, while the long-term frequency stability of B1C/B2a is worse. In addition, the contribution of the differential code bias (DCB) to B2b-RTPPP time transfer is also investigated. The type A uncertainty of the B2b-RTPPP solution without DCB correction is worse than that of the B2b-RTPPP solution with DCB correction. The B1C/B2a B2b-RTPPP solution without DCB correction has better frequency stability than the B1I/B3I B2b-RTPPP solution.