In this work we investigate superconducting properties of niobium samples via application of the muon spin rotation/relaxation (μSR ) technique. We employ for the first time the μSR technique to study samples that are cut out from large and small grain 1.5 GHz radio frequency (rf) single cell niobium cavities. The rf test of these cavities was accompanied by full temperature mapping to characterize the rf losses in each of the samples. Results of the μSR measurements show that standard cavity surface treatments like mild baking and buffered chemical polishing performed on the studied samples affect their surface pinning strength. We find an interesting correlation between high field rf losses and field dependence of the sample magnetic volume fraction measured via μSR . The μSR line width observed in zero-field-μSR measurements matches the behavior of Nb samples doped with minute amounts of Ta or N impurities. A lower and an upper bound for the upper critical field Hc2 of these cutouts is found.