Abstract We conducted a Ka-band (26.1–35 GHz) line survey toward Orion KL using the TianMa 65 m Radio Telescope (TMRT). It is the first blind line survey in the Ka band and achieves a sensitivity at the mK level (1–3 mK at a spectral resolution of ∼1 km s⁻¹). In total, 592 Gaussian features are extracted. Among them, 257 radio recombination lines (RRLs) are identified. The maximum Δn of RRLs of H, He, and C are 20, 15, and 5, respectively. Through stacking, we have detected the β lines of ion RRLs (RRLs of C⁺ with the possible contribution of other ions like O⁺) for the first time, and a tentative signal of the γ lines of ion RRLs can also be seen on the stacked spectrum. Besides this, 318 other line features were assigned to 37 molecular species, and 10 of these species were not detected in the Q-band survey of TMRT. The vibrationally excited states of nine species were also detected. The emission of most species can be modeled under LTE. A number of transitions of E-CH3OH (J ₂ − J ₁) display maser effects, which are confirmed by our modeling, and besides the bumping peak at J ∼ 6, there is another peak at J ∼ 13. Methylcyanoacetylene (CH₃C₃N) is detected in Orion KL for the first time. This work emphasizes that the Ka band, which was long ignored for spectral line surveys, is very useful for surveying RRLs and molecular lines simultaneously.