We present a detailed spectroscopic analysis of RR Lyrae (RRL) variables in the globular cluster NGC 5139 (ω Cen). We collected optical (4580–5330 Å), high-resolution (R ∼ 34,000), high signal-to-noise ratio (∼200) spectra for 113 RRLs with the multifiber spectrograph M2FS at the Magellan/Clay Telescope at Las Campanas Observatory. We also analyzed high-resolution (R ∼ 26,000) spectra for 122 RRLs collected with FLAMES/GIRAFFE at the Very Large Telescope, available in the ESO archive. The current sample doubles the literature abundances of cluster and field RRLs in the Milky Way based on high-resolution spectra. Equivalent-width measurements were used to estimate atmospheric parameters, iron, and abundance ratios for α (Mg, Ca, Ti), iron peak (Sc, Cr, Ni, Zn), and s-process (Y) elements. We confirm that ω Cen is a complex cluster, characterized by a large spread in the iron content: ‑2.58 ≤ [Fe/H] ≤ ‑0.85. We estimated the average cluster abundance as < [{Fe}/{{H}}]> =-1.80+/- 0.03, with σ = 0.33 dex. Our findings also suggest that two different RRL populations coexist in the cluster. The former is more metal-poor ([Fe/H] ≲ ‑ 1.5), with almost solar abundance of Y. The latter is less numerous, more metal-rich, and yttrium enhanced ([Y/Fe] ≳ 0.4). This peculiar bimodal enrichment only shows up in the s-process element, and it is not observed among lighter elements, whose [X/Fe] ratios are typical for Galactic globular clusters. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.