The self-sensing cement composites (SSCC) containing traditional conductive carbon materials are of great significance but cause serious pollution. In this study, the green SSCC is innovatively developed utilizing the synergistic effects of nano carbon black and biochar from coconut shell. The SSCC mixtures are compared in terms of fluidity, mechanical properties, resistivity, microstructure and comprehensive properties. The results indicate that in SSCC containing nano carbon black, the addition of biochar can obtain comparable compressive strength for its internal curing, interlocking and bridging effects. Besides, 4.5 % carbon material prolongs the crack initiation stage during compression, and 9 % carbon material causes the multiple cracks. Moreover, the addition of 4.5 % biochar can reduce the 35-day resistivity of sample with 1.5 % biochar and 3 % nano carbon black by 35.6 % owing to the increasing tunneling effect and contact conduction. It is also found that in conductive SSCC, the slope Kc of the non-contact resistivity curve is dominated by the conductive additives rather than cement hydration. And the self-sensing cement composites exhibit excellent piezoresistivity. The rates of change in resistivity of samples after cycle loading are exponentially related to residual damages, with R2 values greater than 0.95. Finally, multi-indicator evaluation analyses show that the sample containing more biochar is more environmentally friendly. This study provides a new pathway for the sustainable development of SSCC.