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.