The SyntaxError in the second example comes from the fact, that else needs no condition. The first example is totally ok.

Still better, keep the try-block as short as possible:

print("What is 1 + 1?")
while True:
    try:
        UserInput = int(input(("Your answer here:"))
    except ValueError:
        print("That is not a number. Try again!")
    else:
        if UserInput == 2:
            print("Congratulations you are correct!")
            break
        else:
            print("That is incorrect. Try again!")

I think you misunderstand what ValueError (and in general, an Exception) is.

Exceptions are a way for a method to signal to its caller that some critical error condition has been encountered that would prevent that method from executing as intended. Python's try-except-finally control structure provides a way for the caller to detect those error conditions and react accordingly.

ValueError is a standard Exception raised by various methods that perform range-checking of some kind to signal that a value provided to the method fell outside the valid range. In other words, it's a universal way of signaling that error condition. ValueError by itself doesn't do any kind of checking. There are many other standard Exceptions like this; KeyError signifies that you tried to access a key in a mapping structure (like a dict or set) that didn't exist, IndexError means you tried to index into a list-like structure to an invalid location, etc. None of them actually do anything special in and of themselves, they're simply a way of directly specifying exactly what kind of problem was encountered by the called method.

Exceptions go hand in hand with the idiom in python that it is generally considered 'easier to ask forgiveness than permission'. Many languages support exceptions of course, but Python is one of the few where you will very frequently see code where the Exception case is actually a commonly-followed code path rather than one that only happens when something has gone really wrong.

Here is an example of the correct use of a ValueError:

def gen(selection):
    if imode == 0:
        # do EOS stuff here
    elif imode == 1:
        # do S2 stuff here
    else:
        raise ValueError("Please Select An Option Between 0-1")

def selector():
    while True:
        try:
            gen(int(input("Generate for EOS(0) or S2(1)")))
            break
        except ValueError as e: # This will actually satisfy two cases; If the user entered not a number, in which case int() raises, or if they entered a number out of bounds, in which chase gen() raises.
            print(e) 

Note there are probably much more direct ways to do what you want, but this is just serving as an example of how to correctly use a ValueError.

Use try/except.

>>> while True:
...     try:
...         x = int(raw_input("Please enter a number: "))
...         break
...     except ValueError:
...         print "Oops!  That was no valid number.  Try again..."
...

You should use try...except ValueError, as a ValueError is raised when integer cannot convert something to an integer

choice = [1, 2, 3]


def configselect(choice):
    if choice == 1:
        print("you chose 962")
    elif choice == 2:
        print("you chose Audience")
    elif choice == 3:
        print("you chose mAP")
    
while True:
    try:
        val=int(input("Are you configuring a (1)962, (2)Audience, or (3)mAP? "))
        if val in choice:
            configselect(val)
            break
        else:
            print("Please select either 1,2 or 3")
    except ValueError:
        print('Thats not a valid Number. Please try Again.')