The efficiency of sample introduction into the analytical column, during pyrolysis gas chromatography analysis, has a pronounced effect on the quality of the resulting pyrograms. To investigate the effect of pressure programming on the efficiency of sample transfer from the pyrolyzer to the column, experiments were carried out in which either the pressure or the flow rates were kept constant at selected values. In addition, the effect of different pressure pulse sequences was also studied, using in all cases the pyrolysis of d-glucose in the presence of glycine as a model. Total area counts and total number of peaks, were used as indicators of efficiency of sample transfer. Selected reaction products from the beginning, the middle and the end of the chromatograms were used to monitor changes in retention times, resolution (Rs) and the separation number (TZ). The results indicated that the higher values of constant flow rates or constant pressure, increase the total number of peaks and total area counts, at the same time, decreasing the retention times of the peaks. The drop in retention times of the later eluting peaks was higher than the earlier eluting peaks. However, the most efficient sample transfer protocol was found to be the application of a high pressure pulse followed by a drop in pressure to establish an optimum constant flow for the remaining of the chromatographic run.