Equipment consisting of annular denuders, a filter, and a polyurethane foam adsorbent was used for sampling 15 PAHs from the diluted emission from a heat-storing masonry heater. The denuder method was compared to the ISO 11338 method which was used for the sampling from hot and undiluted exhaust gas. The denuder method used with the exhaust dilution gave a realistic gas–particle distribution of PAHs in more atmospheric-like conditions compared to the sampling from undiluted exhaust gas where PAHs were almost totally in the gas phase. The results gained with the denuder method from the diluted exhaust are more relevant, e.g., from exposure and atmospheric processes point of view. The emissions from smoldering combustion conditions (SC) were compared with the emissions from normal combustion conditions (NC). The emission of each PAH was 7 to 14 times higher from SC than from NC, and the gas–particle distribution was shifted towards the particle phase due to increased condensation of PAHs. The PAHs could be divided into three groups based on their phase distributions. In the first group, PAHs existed mostly in the gas phase in both combustion cases; the vapor pressures of PAHs were lower than the saturation vapor pressures. In the second group, the gas phase was saturated and the concentration was almost the same in both combustion cases, whereas the particle phase concentration was higher in SC. In the third group, PAHs were mostly in the particle phase where the concentration was higher in SC.