Yes, the efficiency can be greater than one. (At least, it can in principle - I'm not aware of any experimental verification of this at the present time.)
One way to define temperature is as follows:
$$
\frac{1}{T} = \frac{\partial S}{\partial U}.
$$
This means that if $T$ is negative then the entropy increases when you take energy out of the system. Therefore, in principle, you can take heat out of a negative-temperature system and convert it directly into work without violating the second law. But this is an irreversible process (it increases the entropy), so in theory you can even do even better - you can take energy out of some other reservoir (at a positive temperature) in order to offset the entropy increase and end up with a reversible process.
If you could solve the (probably formidable) technical issues involved in doing this, you'd end up with a heat engine that can take $Q$ units of heat out of the negative-temperature reservoir at $T_-$, and take $-Q\frac{T+}{T_-}>0$ units of heat out of the positive-temperature reservoir, and turn it all into $W\left(1-\frac{T_+}{T_-}\right)Q$ units of work. Since $W>Q$ in this case we can say that this engine has an efficiency greater than 1, without breaking the second law.
By the way, note that $T_-$ plays the role of the hot reservoir in this engine, not the cold reservoir. Negative temperatures are hotter than positive temperatures, which is really just a consequence of the definition above.
In his answer, gatsu quite rightly mentions the debate about whether negative temperatures exist at all. (I'm very much in the camp that says they do.) If there were an experimental demonstration of this greater-than-unity efficiency effect then that would just about wrap this debate up - but as I said, I think the technical challenges involved in doing so are probably quite extreme.