Indoor air pollution has been recognized as an important risk factor for human health, especially in areas where people tend to spend most of their time indoors. Many semivolatile organic compounds (SVOCs) have primarily indoor sources and are present in orders of magnitudes higher concentrations indoors than outdoors. Despite this, awareness of SVOCs in indoor air and assessment of the link between indoor concentrations and human health have lagged behind that of outdoor air. This is partially related to challenges with indoor sampling of SVOCs. Passive air samplers (PASs), which are widely accepted in established outdoor air monitoring networks, have been used to fill the knowledge gaps on indoor SVOCs distribution. However, their applicability for indoor environments and the assessment of human health risks has not yet been supported with sufficient experimental data. To address this issue, we performed an indoor calibration study of polyurethane foam (PUF) PAS covering both legacy and new SVOC classes. PUF-PAS and continuous low-volume AAS were co-deployed for a calibration period of twelve weeks. Based on the results from this evaluation, PUF-PAS is recommended for indoor sampling and health risk assessment of gas phase SVOCs, including novel brominated flame retardants (nBFR). Data for particle associated SVOCs suffer from significant uncertainties caused by low level of detection and low precision. In such cases, PAS should be accompanied by complementary sampling techniques.