Updated for Numpy 1.7.0:(Hat-tip to @Rolf Bartstra.)
a=np.empty(n); a.fill(5) is fastest.
In descending speed order:
%timeit a=np.empty(1e4); a.fill(5)
100000 loops, best of 3: 5.85 us per loop
%timeit a=np.empty(1e4); a[:]=5
100000 loops, best of 3: 7.15 us per loop
%timeit a=np.ones(1e4)*5
10000 loops, best of 3: 22.9 us per loop
%timeit a=np.repeat(5,(1e4))
10000 loops, best of 3: 81.7 us per loop
%timeit a=np.tile(5,[1e4])
10000 loops, best of 3: 82.9 us per loop