The transfer function method recommended by the ASHRAE can be considered the most modern tool currently available for the thermal analysis of a building. It is particularly well suited for use with a computer as it makes it possible to describe with great accuracy the internal heat gain of walls using a small set of coefficients. The present paper shows how to calculate sets of coefficients diverse from that proposed by Mitalas who first developed the method and on the basis of an unequivocal criterion, to prove the advantages in using them. The authors also investigated some of the paramount mathematical and physical aspects which affect the approximation degree of the ASHRAE method and, with reference to the optimal number of poles and coefficients, they tried to offer some certainties for a more conscious use of it.