see docs: http://pandas.pydata.org/pandas-docs/stable/generated/pandas.DataFrame.insert.html
using loc = 0 will insert at the beginning
df.insert(loc, column, value)
df = pd.DataFrame({'B': [1, 2, 3], 'C': [4, 5, 6]})
df
Out:
B C
0 1 4
1 2 5
2 3 6
idx = 0
new_col = [7, 8, 9] # can be a list, a Series, an array or a scalar
df.insert(loc=idx, column='A', value=new_col)
df
Out:
A B C
0 7 1 4
1 8 2 5
2 9 3 6