You're only adding one variable to the table. That means the length of the table will always be one, which means math.random(1,#a) will always return one. Additionally, you're only calling random once, which means once the random value for b is chosen, it will always be the same.
Once you've fixed these errors, you might notice your code isn't very efficient. For instance, you have 1/4 odds of your random statement picking any one number to print, but instead of 1/4 you're using 250/1000, which is the same but less efficient. Secondly, you can use a table to store the values you want to print and index them with a random number, instead of using a different if statement for each one.
local function Start()
local tab = {"A","B","C","D"}
print tab[math.random(1,#tab)]
end
script.Parent.MouseButton1Click:connect(Start)