We present the first results of a pilot program to conduct an Atacama Large Millimeter Array (ALMA) band10 spectral line survey of the high-mass star-forming region NGC 6334I. The observations were taken in exceptional weather conditions (0.19 mm precipitable water) with typical system temperatures T sys <950K at ∼890GHz. A bright, bipolar north-south outflow is seen in HDO and CS emission, driven by the embedded massive protostar MM1B. This has allowed, for the first time, a direct comparison of the thermal water in this outflow to the location of water maser emission from prior 22GHz Very Large Array observations. The maser locations are shown to correspond to the sites along the outflow cavity walls, where high-velocity gas impacts the surrounding material. We also compare our new observations to prior Herschel Heterodyne Instrument for the Far-infrared (HIFI) spectral line survey data of this field, detecting an order of magnitude more spectral lines (695 versus 65) in the Atacama Large Millimeter/submillimeter Array (ALMA) data. We focus on the strong detections of the complex organic molecule glycolaldehyde (HC(O)CH 2 OH) in the ALMA data that is not detected in the heavily beamdiluted HIFI spectra. Finally, we stress the need for dedicated THz laboratory spectroscopy to support and exploit future high-frequency molecular line observations with ALMA.