Double-pulse LIBS and ED XRF usabilities for quantitative analysis of Ti in samples of cotton, wool, and viscose fabrics were compared to each other. The analyzed samples were prepared by stippling a particular fabric with TiO2 nanoparticle sol (particle size 100 nm). Both spectrometers were calibrated with the aid of the same sets of authentic fabric samples previously analyzed by ICP OES after ... [Show full abstract] the microwave digestion. Average values of the Ti concentration calculated from five repeated measurements of the same sample obtained by LIBS and ED XRF were comparable for all types of the tested materials (100∙(CTi-LIBS/CTi-ED XRF)) ≅ 96–109%), but the precision of analysis expressed as RSD (relative standard deviation) was usually better for ED XRF (RSDLIBS from 9 to 25%, RSDED XRF from 3 to 17%). Poor RSD values of LIBS measurements were observed mainly in the case of samples with lower areal weights. Limits of detection calculated as a triple standard deviation of five repeated measurements of Ti in a sample with the low concentration of the analyte were comparable for both methods (LODLIBS = from 15 to 97, and LODED XRF = from 21 to 64, all in mg/kg).