If you really want a matrix, you might be better off using numpy. Matrix operations in numpy most often use an array type with two dimensions. There are many ways to create a new array; one of the most useful is the zeros function, which takes a shape parameter and returns an array of the given shape, with the values initialized to zero:

>>> import numpy
>>> numpy.zeros((5, 5))
array([[ 0.,  0.,  0.,  0.,  0.],
       [ 0.,  0.,  0.,  0.,  0.],
       [ 0.,  0.,  0.,  0.,  0.],
       [ 0.,  0.,  0.,  0.,  0.],
       [ 0.,  0.,  0.,  0.,  0.]])

Here are some other ways to create 2-d arrays and matrices (with output removed for compactness):

numpy.arange(25).reshape((5, 5))         # create a 1-d range and reshape
numpy.array(range(25)).reshape((5, 5))   # pass a Python range and reshape
numpy.array([5] * 25).reshape((5, 5))    # pass a Python list and reshape
numpy.empty((5, 5))                      # allocate, but don't initialize
numpy.ones((5, 5))                       # initialize with ones

numpy provides a matrix type as well, but it is no longer recommended for any use, and may be removed from numpy in the future.

A pattern that often came up in Python was

bar = []
for item in some_iterable:
    bar.append(SOME EXPRESSION)

which helped motivate the introduction of list comprehensions, which convert that snippet to

bar = [SOME_EXPRESSION for item in some_iterable]

which is shorter and sometimes clearer. Usually, you get in the habit of recognizing these and often replacing loops with comprehensions.

Your code follows this pattern twice

twod_list = []                                       \                      
for i in range (0, 10):                               \
    new = []                  \ can be replaced        } this too
    for j in range (0, 10):    } with a list          /
        new.append(foo)       / comprehension        /
    twod_list.append(new)                           /