Just keep track of index using enumerate and get the previous item by index
li = list(range(10))
for i, item in enumerate(li):
if i > 0:
print(item, li[i-1])
print("or...")
for i in range(1, len(li)):
print li[i], li[i-1]
Output:
1 0
2 1
3 2
4 3
5 4
6 5
7 6
8 7
9 8
or...
1 0
2 1
3 2
4 3
5 4
6 5
7 6
8 7
9 8
Another alternative is to remember the last item, e.g.
last_item = None
for item in li:
print(last_item, item)
last_item = item