For me it typically take from 2-4 hours before the Libre results are spot on. It always starts out reporting in the low end. Most often like 2-3 mmol/dl too low, at times up to 4-5 mmol/dl too low. It then become more and more accurate within the following 2-4 hours. As noted by other posters, can only consider its because it has to accommodate to your 'skin temperature' (Have at times plugged a new sensor direct from e.g. a frozen car and that showed lowest and most off the scale of any I tried so far ;o). Likewise it also need to be getting nurtured in its new home for the next 14 days before it will get all the sugars etc floating freely around the sensor needle tip. It is a foreign subject we plunge into the arm, so potentially a minor rupture in supporting tissue has to be overcome before metabolism and fluid perfusion near and around the sensor is back to normal.
Been using it for more than 1 year now. Have not used a 'normal' finger prick + bg meter for last 9 months now, so fully reliant on- and trusting my life on this new gadget. ;o)
Diving, surfing, paragliding, skiing, weekly airplane flights, 4 continents, 25+ countries. High, low, warm, cold, dry or wet. It's been through the paces with me and shown to be working consistently well and deserve my trust. Had only two sensor going bad, and every time my own fault.