The establishment of CFC-free polyurethane foam systems, aimed at total CFC elimination by the year 1995, is of paramount importance in the present day polyurethane foam technology. Especially in rigid foam systems, the attempts to apply a variety of alternative blowing agents such as HCFC-22, -141b, and -142b, HFC-134a and -356, and hydrocarbons such as n-pentane, isopentane and cyclopentane, as well as all-water blown systems, are being examined. In all cases of alternative blown systems, however, there exist differences in foaming behavior as well as inferior foam properties compared to traditional CFC-11 blown systems. Especially in HCFC-141b and cyclopentane blown systems, which have gained the greatest interest among the above-mentioned options, the following three subjects are of major concern. The requirements involved in achieving the resolution of these problems are dependent not only on the development of major raw materials but also on the selection of suitable auxiliary intermediates such as catalysts and foam stabilizers. (1) Thermal Conductivity; HCFC-141b, cyclopentane and carbon dioxide, which is generated from the reaction of water and isocyanate, have high thermal conductivity compared to CFC-11, thereby causing inferior insulation performance of the foam. Fine cell technology is now being examined in order to improve the thermal conductivity. For the achievement of the fine cell structure, the selection of suitable amine catalyst systems is important, although the effect of foaming stabilizers has an especially large contribution. (2) Dimensional Stability; not only in all-water blown systems, but also in HCFC-141b and cyclopentane blown systems which use water in high concentration, dimensional stability becomes a large problem due to the diffusion of carbon dioxide gas from the foam cell. For the improvement of dimensional stability, there exists the option to increase the foam strength; moreover, it is important to improve the isotropy of cell structure by adjusting amine catalyst systems. (3) Foam density; since 141b and cyclopentane have relatively higher boiling points and less blowing efficiency, lowering the foam density becomes rather difficult. Moreover, lower foam density normally provides poor dimensional stability. It can be said that the catalytic activity ratio in blowing/gelling of amine catalysts play an important role for the lowering of foam density with improved dimensional stability. It is very difficult to improve these three factors simultaneously. In this report, however, the improvements of these subjects are discussed from a standpoint of amine catalysts; also special newly developed nucleation catalyst systems are introduced for cyclopentane and HCFC-141b blown systems.