Abstract Cold sintering is a promising technology for preparing electronic materials, enabling densification at low temperature, but rarely employed for thermoelectrics. Herein, high-quality Ca2.7Bi0.3Co3.92O9+δ ceramics were synthesised by a combination of cold sintering and annealing processes. Stoichiometric mixtures of raw materials were calcined once or twice at 1203 K for 12 h in air, and then cold sintered at 673 K for 60 min under a pressure of 85 MPa, followed by annealing at 1203 K for 12 h or 24 h in air. The effects of the calcination processes and annealing conditions on the thermoelectric performance of cold sintered samples were investigated. By optimising heat-treatment, the formation of secondary phases, texture development and porosity were controlled, leading to enhanced electrical conductivity and reduced thermal conductivity. Consequently, at 800 K there was 85% increase in power factor and 35% increase in ZT (value of 0.15) compared to previous studies.