This paper investigates the electrical, thermal and mechanical properties as well as the environmental performance of polymer cementitious composites (PCCs) as sustainable coating materials for underground power cables and as high-voltage insulators. Particular focus is placed on the optimised mix design and the effect of the manufacturing method on the performance of PCCs, incorporating liquid styrene and acrylic (SA) monomers, wollastonite and muscovite. Microstructural investigations, together with results from strength tests, indicate that the manufacturing method is a key performance parameter. Experimental results show that PCC mixes containing 25% SA emulsion, 12.5% wollastonite and no muscovite provide the most favourable dielectric properties from the mixes investigated. The PCC material has a dielectric strength up to 16.5 kV/mm and a dielectric loss factor lower than 0.12. Additional experiments also show that PCC has good thermal stability and thermal conductivity. The mechanical strength tests indicate that PCC specimens possess reliable strengths which are applicable in structural design. Environmental assessments also show that PCCs possess significantly lower embodied energy and embodied carbon than conventional plastic insulating materials.