The physico-chemical and application properties of phenol-formaldehyde resins used in the production of laminated plastics depend on such factors as: type and amount of catalyst, formaldehyde-to-phenol mole ratio, temperature and time of the synthesis process. The special impact on the reaction mechanism and kinetics, e.g. on the formation of mono-, di- and trihydroxymethyl derivatives of phenol (PhOH) is a consequence of the type and amount of the catalyst. This paper presents the results of optimisation research of resol resin synthesis catalysed by trimethylamine (TEA) carried out according to 32 experimental design. The aim of the research was to determine the synthesis conditions under which it is possible to achieve products with reduced content of unconverted formaldehyde (CH2O), phenol and its hydroxymetyl derivatives, while maintaining the required physico-chemical properties. The process employing selected polyamines as well as TEA together with polyamine co-catalysts i.e. diethylenetriamine (DETA) and triethylenetetraamine (TETA) was also studied. The results were compared with those of the resins which were synthesised with the use of classic catalysts-ammonia (NH3) and triethylamine for which the content of CH2O, PhOH and its hydroxymethyl derivatives was respectively: NH3-5.13% and 46.27%, TEA-0.33% and 52.41%. In the case DETA was added, the content of phenol and its hydroxymethyl derivatives could be reduced by 52.49% in relation to the resin obtained with the use of TEA and by 46.19% in relation to the resin obtained with the use of ammonia. The formaldehyde content was reduced by 78.79% and 98.64%, respectively. When TETA was added as a co-catalyst, the content of phenol and its derivatives was reduced by 48.04% versus triethylamine-catalysed resin and by 41.15% versus ammonia-catalysed material. The reduction in formaldehyde content reached 84.85% and 99.03%, respectively. The results of kinetic study were also presented, the prediction accuracy of the proposed kinetic model is more than 98% for all the catalysts in the state variable space. Polyamine co-catalysts gave much higher rate constants (0.50 and 0.45 for TETA and DETA, respectively).