Novel microwave discharge granulated electrodeless lamps (MDGELs; 5mm×10mm), fabricated using vacuum-UV (VUV) transparent quartz envelopes, have been examined for the treatment of model contaminated wastewaters. Evaluation of these MDGELs was performed through the self-ignition of the lamps at low microwave power levels and by the photoassisted decomposition and defluorination of trifluoroacetic acid (TFA), heptafluorobutyric acid (HFBA) and perfluorooctanoic acid (PFOA) in aqueous solutions in a flow-through microwave photoreactor (MW/Photo) containing 20 such MDGELs. A conventional single rod-shaped microwave discharge electrodeless lamp (MDEL) and a low-pressure electrode Hg lamp were also used to compare the performance of these novel MDGELs. The dominant performance of the MDGELs was established by the defluorination kinetics per surface area of the light source immersed in the solutions and by the applied electric power of the lamps. At pH 10, the kinetics correlated with the carbon chain length and with the number of C–F bonds in the three fluorinated acids. Microwave irradiation of the single rod-shaped MDEL device achieved a defluorination level of 51% (TFA), 67% (HFBA), and 37% (PFOA) for a 240-min VUV/UV irradiation of solutions at initial pHs=4.7–5.2, whereas at pH=10 defluorination of TFA and HFBA was 100% complete within 120–135min of irradiation; defluorination of PFOA was ca. 80% complete after 200min. With the 20 MDGEL system, 100% defluorination of TFA and HFBA was achieved after 105min, whereas 100% defluorination of PFOA required ca. 400min of irradiation. A decomposition/defluorination pathway is described for PFOA on the basis of intermediates identified by LC–MS techniques that involved initial VUV/UV irradiation (185nm and 254nm) of the PFOA contaminant followed by subsequent losses of CO2 and –CF2 units to complete defluorination and degradation.