We present a catalogue of 12.2-GHz methanol masers detected towards 6.7-GHz methanol masers observed in the unbiased Methanol Multibeam (MMB) survey in the longitude range 330° (through 360°) to 10°. This is the first portion of the catalogue which, when complete, will encompass all of the MMB detections. We report the detection of 185 12.2-GHz sources towards 400 6.7-GHz methanol maser targets, equating to a detection rate of 46 per cent. Of the 185 12.2-GHz detections, 118 are reported here for the first time. We draw attention to a number of ‘special’ sources, particularly those with emission at 12.2-GHz stronger than their 6.7-GHz counterpart, and conclude that these unusual sources are not associated with a specific evolutionary stage.