As an advanced clean coal combustion technology, pressurized coal combustion in a fluidized bed has gained much attention with respect to both pressurized fluidized bed combustor/combined cycle and pressurized oxy-fuel combustion for CO2 capture. However, there has been no study on sulfur in particulate matter (PM) under this scenario. Therefore, a 10 kW(th) continuous coal feeding lab-scale pressurized fluidized bed combustor system equipped with an electrical low-pressure impactor for PM sampling was established, and coal samples with two different sizes were tested at 0.3 and 0.5 MPa, respectively. In this paper, the sulfur fate during pressurized combustion was focused, particularly on its occurrence and enrichment in PM. It was found that sulfur shows an identifiable enrichment in sub-micrometer particles when the operating pressure is 0.5 MPa or the coal particle size is larger. Sulfur did not enrich in sub-micrometer PM for smaller coal particles under 0.3 MPa. Furthermore, sulfur was likely to be enriched in PM0.4 in the form of sulfide or organic sulfur when coarse fuel particles were used under the same pressure. For the same small-size coal, sulfur was transformed into calcium sulfate in sub-micrometer particles when the pressure was elevated from 0.3 to 0.5 MPa.