The fundamental mechanisms of heat transfer through rigid polyurethane (PUR) foam are reviewed in terms of three distinct elements, λg, λs and λr, which represent heat transfer by thermal conductivity through the gas phase, solid phase and by radiation respectively. It is demonstrated that values for λg and λs can be estimated, and from the measured λ-value of the foam, an approximation of λr obtained by difference. This shows that there is considerable scope for improving the thermal insulation efficiency of these materials. Small reductions in λ-value can be obtained by optimisation of λg and λs elements, but the main scope for improvement is by reduction of λr This can be partially achieved by the production of foam with very fine cells. However there are strong indications that the cell windows are transparent to radiative heat transfer and several other factors need to be taken into account in reducing λr to its minimum practical value. Combining all these factors, laboratory foams can be produced consistently with λ-values 20–30% lower than typical commercial material. Ageing of the λ-value, which results from air ingress into the cells of the foam, can be substantially eliminated by covering the foam with air-impermeable barriers. However recent developments have shown that by optimisation of foam formulations, the rate of ageing and the aged λ-value can also be significantly reduced in uncovered foams. The excellent insulation properties of PUR foams compared with competitive materials is a consequence of the low value of λg, which results from the encapsulation of the Refrigerant 11 blowing agent inside the foam cells. Supplies of Refrigerant 11 may become limited in the future, with potential adverse effects on the insulation efficiency of PUR foam. In such a situation the indications are that any losses in insulation efficiency can be minimised and be more than compensated for by further optimisation of the approaches discussed in this paper.