First, your regex doesn't even attempt to capture anything but four dotted numbers, so of course it's not going to match anything else, like a /32 on the end. if you just add, e.g., /\d{1,2} to the end, it'll fix that:
(?:\d{1,3}\.){3}\d{1,3}/\d{1,2}

Debuggex Demo
However, if you don't understand regular expressions well enough to understand that, you probably shouldn't be using a regex as a piece of "magic" that you'll never be able to debug or extend. It's a bit more verbose with str methods like split or find, but maybe easier to understand for a novice:
for line in file:
for part in line.split()
try:
address, network = part.split('/')
a, b, c, d = address.split('.')
except ValueError:
pass # not in the right format
else:
# do something with part, or address and network, or whatever
As a side note, depending on what you're actually doing with these things, you might want to use the ipaddress module (or the backport on PyPI for 2.6-3.2) rather than string parsing:
>>> import ipaddress
>>> s = '10.1.1.1/32'
>>> a = ipaddress.ip_network('10.1.1.1/32')
You can combine that with either of the above:
for line in file:
for part in line.split():
try:
a = ipaddress.ip_network(part)
except ValueError:
pass # not the right format
else:
# do something with a and its nifty methods
/32or similar at the end, so of course it's only going to match the10.1.1.1or similar.re.findall("\d+\.\d+\.\d+\.\d+\/\d+",file.read()), you should also usewithto open your filesreadlines()there.fileis already an iterable of lines. All you're doing is wastefully forcing Python to read and parse the entire file in memory before you can use it.