The technique of carrier phase (CP), based on the global navigation satellite system (GNSS), has proven to be a highly effective spatial tool in the field of time and frequency transfer with sub-nanosecond accuracy. The rapid development of real-time GNSS satellite orbit and clock determinations has enabled GNSS time and frequency transfer using the CP technique to be performed in real-time mode, without any issues associated with latency. In this contribution, we preliminarily built the prototype system of real-time multi-GNSS time and frequency transfer service in National Time Service Center (NTSC) of the Chinese Academy of Sciences (CAS), which undertakes the task to generate, maintains and transmits the national standard of time and frequency UTC(NTSC). The comprehensive assessment of the availability and quality of the service system were provided. First, we assessed the multi-GNSS state space representation (SSR) correction generated in real-time multi-GNSS prototype system by combining broadcast ephemeris through a comparison with the GeoForschungsZentrum (GFZ) final products. The statistical results showed that the orbit precision in three directions was smaller than 6 cm for global positioning system (GPS) and smaller than approximately 10 cm for BeiDou satellite system (BDS). The root mean square (RMS) values of clock differences for GPS were approximately 2.74 and 6.74 ns for the GEO constellation of BDS, 3.24 ns for IGSO, and 1.39 ns for MEO. The addition, the GLObal NAvigation Satellite System (GLONASS) and Galileo satellite navigation system (Galileo) were 4.34 and 1.32 ns, respectively. In order to assess the performance of real-time multi-GNSS time and frequency transfer in a prototype system, the four real-time time transfer links, which used UTC(NTSC) as the reference, were employed to evaluate the performance by comparing with the solution determined using the GFZ final products. The RMS could reach sub-nanosecond accuracy in the two solutions, either in the SSR or GFZ solution, or in GPS, BDS, GLONASS, and Galileo. The frequency stability within 10,000 s was 3.52 × 10−12 for SSR and 3.47 × 10−12 for GFZ and GPS, 3.63 × 10−12 for SSR and 3.53 × 10−12 for GFZ for BDS, 3.57 × 10−12 for SSR and 3.52 × 10−12 for GFZ for GLONASS, and 3.56 × 10−12 for SSR and 3.48 × 10−12 for GFZ for Galileo.