In recent years, fossil fuel emissions and human activities have generated a lot of heat energy, causing environmental temperatures to rise. Thermoelectric cementitious composites that use temperature difference power generation to achieve the transformation of thermal and electrical energy can achieve a reduction in urban environmental temperature and alleviate resource depletion. However, the low thermoelectric conversion efficiency at this stage restricts its development. In this paper, boron‐doped carbon nanotubes (B‐CNTs) are proposed to improve the thermoelectric properties of cement materials by doping boron into carbon nanotubes through the thermal diffusion method. At H3BO3: CNTs = 1:4, the synthesized boron‐doped carbon nanotubes improved the Seebeck coefficient, which was mainly due to the increase in defect content and the appearance of additional phases around the Fermi energy level, leading to enhanced thermoelectric properties due to the increase in carrier scattering intensity. The thermoelectric optimum of the cement matrix composite with 7.0 wt% boron‐doped carbon nanotube content was 1.1×10‐4, which was three times higher than that of the undoped carbon nanotube. This paper provides a research idea to modify the thermoelectric properties of the material by doping the carbon material.This article is protected by copyright. All rights reserved.