We have examined methanol emission from Orion KL with the Herschel/HIFI instrument, and detected two methanol bands centered at 524 GHz and 1061 GHz. The 524 GHz methanol band (observed in HIFI band 1a) is dominated by the isolated ΔJ = 0, K = −4 → −3, vt = 0 Q branch, and includes 25 E-type and 2 A-type transitions. The 1061 GHz methanol band (observed in HIFI band 4b) is dominated by the ΔJ = 0, K = 7 → 6, vt = 0 Q branch transitions which are mostly blended. We have used the isolated E-type vt = 0 methanol transitions to explore the physical conditions in the molecular gas.With HIFI’s high velocity resolution, the methanol emission contributed by different spatial components along the line of sight toward Orion KL (hot core, low velocity flow, and compact ridge) can be distinguished and studied separately. The isolated transitions detected in these bands cover a broad energy range (upper state energy ranging from 80 K to 900 K), which provides a unique probe of the thermal structure in each spatial component. The observations further show that the compact ridge is externally heated. These observations demonstrate the power of methanol lines as probes of the physical conditions in warm regions in close proximity to young stars.