Emission of semivolatile organic compounds (SVOCs) from source materials usually occurs very slowly in indoor environments due to their low volatility. When the SVOC emission process is controlled by external mass transfer, the gas-phase concentration in equilibrium with the material ( y0) is used as a key parameter to simplify the source models that are based on solid-phase diffusion. A material-air-material (M-A-M) configured microchamber method was developed to rapidly measure y0 for a polyisocyanurate rigid foam material containing organophosphate flame retardants (OPRFs). The emission test was conducted in 44 mL microchambers for target OPFRs, including tris(2-chloroethyl) phosphate (CASRN: 115-96-8), tris(1-chloro-2-propyl) phosphate (CASRN: 13674-84-5), and tris(1,3-dichloro-2-propyl) phosphate (CASRN: 13674-87-8). In addition to the microchamber emission test, two other types of tests were conducted to determine y0 for the same foam material: OPFR diffusive tube sampling tests from the OPFR source foam using stainless-steel thermal desorption tubes and sorption tests of OPFR on an OPFR-free foam in a 53 L small chamber. Comparison of parameters obtained from the three methods suggests that the discrepancy could be caused by a combination of theoretical, experimental, and computational differences. Based on the y0 measurements, a linear relationship between the ratio of y0 to saturated vapor pressure concentration and material-phase mass fractions has been found for phthalates and OPFRs.