Abstract We performed a radio recombination line (RRL) survey to construct a high-mass star-forming region (HMSFR) sample in the Milky Way based on the all-sky Wide-Field Infrared Survey Explorer point-source catalog. The survey was observed with the Shanghai 65 m Tianma radio telescope covering 10 hydrogen RRL transitions ranging from H98 α to H113 α (corresponding to the rest frequencies of 4.5–6.9 GHz) simultaneously. Out of 3348 selected targets, we identified an HMSFR sample consisting of 517 sources traced by RRLs; a large fraction of this sample (486) is located near the Galactic Plane (∣ b ∣ < 2°). In addition to the hydrogen RRLs, we also detected helium and carbon RRLs toward 49 and 23 sources, respectively. We crossmatch the RRL detections with the 6.7 methanol maser sources built up in previous works for the same target sample. As a result, 103 HMSFR sources were found to harbor both emissions. In this paper, we present the HMSFR catalog accompanied by the measured RRL line properties and a correlation with our methanol maser sample, which is believed to trace massive stars at earlier stages. The construction of an HMSFR sample consisting of sources in various evolutionary stages indicated by different tracers is fundamental for future studies of high-mass star formation in such regions.