You had your lines the wrong way around, you need:
dic[raw_input("Enter the access key of a value: ")] = input("Enter the value you want to store: ")
Not
dic[raw_input("Enter the value you want to store: ")] = input("Enter the access key of a value: ")
So complete code would be:
while 1:
dic = {} #empty dictionary which will be used for storing all the data
dic[raw_input("Enter the access key of a value: ")] = input("Enter the value you want to store: ")
ans = raw_input("Exit:e ; Store another variable : s; Acces a variable: a")
if ans=="e":
break; #exit the main loop
elif ans == "s":
continue;
elif ans=="a":
pass;