Assuming that you are dealing only with positive numbers, you can divide each number by the greatest power 10 less than the number, and then take the word of result.
>>> from math import log10, floor
>>> lst = [34523, 55, 65, 2]
>>> [floor(x / (10**floor(log10(x)))) for x in lst]
[3, 5, 6, 2]
If you use Python 3 instead of overtaking the result, you can use the integer division operator //:
>>> [x // (10**floor(log10(x))) for x in lst]
[3, 5, 6, 2]
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>>> [int(str(x)[0]) for x in lst]
[3, 5, 6, 2]
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