Primary and secondary emissions of volatile organic compounds (VOCs) and polycyclic aromatic hydrocarbons (PAHs) from a waterproof coal tar membrane and their effect on the indoor air quality were investigated through a case study in a residential building situated in Madrid, Spain. The air contaminants were analyzed in situ using photoionization method and several samples of contaminants were taken using three sorbents: activated carbon, XAD2 and Tenax GR. It was found that various VOCs such as toluene, p- and m-Xylene, PAHs such as naphthalene, methyl-naphthalenes, acenaphthene, acenaphthylene, phenanthrene and fluorine, volatile organic halogens including chloroform and trichlorofluoromethane, and alkylbenzene (1,2,4-trimethylbenzene) were found at concentrations, which exceeded the limits established by international and national agencies (WHO, EPA, OSHA). Some of the above organic compounds were found also in the samples of construction and building materials, which were obtained at different heights and places. The analysis of possible sources of the contaminants pointed at the original coal-tar membrane, which was applied on the terrace to be waterproof. During a posterior reparation the membrane was coated with a new one that hindered dissipation of emitted contaminants. The contaminants leached out and were absorbed by construction materials down in the dwelling. These materials then acted as secondary emission sources. To remediate the emission problem as the contaminated materials were removed and then a ventilation system was installed to force the gasses being emitted from the rest of contaminated slab outside. Follow-up has validated the success of the remediation procedure.