Inorganic chalcogenides are traditional high-performance thermoelectric materials. However, they suffer from intrinsic brittleness and it is very difficult to obtain materials with both high thermoelectric ability and good flexibility. Here, we report a flexible thermoelectric material comprising highly ordered Bi2Te3 nanocrystals anchored on a single-walled carbon nanotube (SWCNT) network, where a crystallographic relationship exists between the Bi2Te3 <
$$\bar{1}2\bar{1}0$$
> orientation and SWCNT bundle axis. This material has a power factor of ~1,600 μW m−1 K−2 at room temperature, decreasing to 1,100 μW m−1 K−2 at 473 K. With a low in-plane lattice thermal conductivity of 0.26 ± 0.03 W m−1 K−1, a maximum thermoelectric figure of merit (ZT) of 0.89 at room temperature is achieved, originating from a strong phonon scattering effect. The origin of the excellent flexibility and thermoelectric performance of the Bi2Te3–SWCNT material is attributed, by experimental and computational evidence, to its crystal orientation, interface and nanopore structure. Our results provide insight into the design and fabrication of high-performance flexible thermoelectric materials. Bi2Te3 materials suffer from brittleness, limiting their application for thermoelectric harvesting. By depositing ordered nanocrystals onto single-wall carbon nanotubes, a flexible material is formed that achieves ZT of 0.89 at room temperature.