A Python list has ['12:30','12:45'] and I want to access the '12:30' for the first iteration, and on the second iteration I should get '12:45'.

my_list=['12:30','12:45']
for each_value in my_list:print(each_value[0])

The expected result is '12:30' but the actual output is '1'.

You should write it as:

>>> my_list=['12:30','12:45']
>>> for each_value in my_list:
...     print(each_value)
...
12:30
12:45

each_value is a string "12:30", "12:45" as you move on. So calling [0] on a string will you get the first character of that string which is "1".