That right there is a technique called dynamic programming (aka. memoisation), whereby you store and reuse computed results. This makes lookup and computation much, much faster later on.
When you remove fibValue[n] = result, you don't store the result, and by not storing the result, you need to recompute the fibonacci for that particular number n.
Consider computing fib(6). On the first function call, you get
fib(6) = fib(5) + fib(4)
By recursion, this gives
fib(6) = fib(4) + fib(3) + fib(3) + fib(2)
fib(6) = fib(3) + fib(2) + fib(2) + fib(1) + fib(2) + fib(1) + fib(1) + fib(0)
fib(6) = fib(2) + fib(1) + fib(1) + fib(0) + fib(1) + fib(0) + fib(1) + fib(1) + fib(0) + fib(1) + fib(1) + fib(0)
fib(6) = fib(1) + fib(0) + fib(1) + fib(1) + fib(0) + fib(1) + fib(0) + fib(1) + fib(1) + fib(0) + fib(1) + fib(1) + fib(0)
fib(6) = 1 + 1 + 1 + 1 + 1 + 1 + 1 + 1 + 1 + 1 + 1 + 1 + 1
fib(6) = 13
You could see that fib(3) and fib(2) were computed at least 3 times each. Now consider if your input is much bigger (say 1000). You'd be computing fib(3), fib(100), fib(200), etc. repeatedly. This wastes a huge amount of time. Thus, to save time (since we're programmers, we're very woo about time), we trade in space (i.e. memory) to cache previous computations and thus... save time by doing lookup on the cache.
The time complexity of performing lookup on a Python dictionary is (on average) O(1), this takes constant time, and is the best thing a programmer might wish for in an algorithm. Compare that to the unwieldy time complexity of computing a fib(n) from scratch. (Note that, as @brunodesthuilliers commented, your function currently performs lookup by iterating through a dict.keys() object, which will result in a (worse-case) O(n) time-complexity for lookup. Simply changing if n in fibValue.keys() to if n in fibValue may result in faster computation.)
As suggested by @PatrickArtner, if you're only finding a single fibonacci value, you could make your fibonacci calculator more efficient time-and-space-wise by only storing two values (i.e. the most recent fib values) instead of caching every result.