Otago with 10 points leapfrogged Rajasthan Royals who are on eight points but have played a game less.
Lions are out of the tournament having lost three consecutive matches.
Both teams scored 13 runs in the super over but Otago won by the virtue of losing no wickets to Lions two.
Lions, though, had only themselves to blame for the defeat, twice giving away the initiative. They first let Otago come back into the game after restricting them to 103 for six in 15 overs.
Even after the match went into the super over, the Lions were in the driving seat needing just four runs from four balls. But their overconfidence and lackadaisical approach proved to be their downfall.
Earlier, Quinton de Kock struck a brilliant unbeaten 109 off 63 balls, including 10 fours and five sixes, to help his team score 167 for four. In reply, Otago lost wickets at regular intervals and it seemed they would be bowled out.
However, a late flourish from James Neesham (52 off 25 balls) brought his team back in the fray.
Requiring 50 off the last four overs, Otago looked down and out. Neesham smacked Lonwabo Tsotsobe for 18 runs to bring the equation down to 32 off 18 balls.
Another 12 runs off the next over meant Otago were well and truly back in the match. Needing 11 off the final over, Neesham cleared the boundary with ease in the first ball to put the New Zealand team in the driving seat.
Pakistan pacer Sohail Tanvir held his nerve to restrict the marauding Neesham in the last five balls, taking the match into super over.
Highveld Lions 167 for four in 20 overs (Quinton de Kock 109 not out, Jean Symes 20; Nick Beard 2-31) vs Otago Volts 167 for seven in 20 overs (James Neesham 52 not out, Hamish Rutherford 32; Lonwabo Tsotsobe 2-30, Imran Tahir 2-28)
--IANS (Posted on 29-09-2013)