Theoretical probability is what we compute from an idealized model. A fair coin has by symmetry; a fair die has . We never had to flip the coin to know that.
Empirical probability is what we estimate from data. Flip a real coin 1,000 times, count the heads, and divide by 1,000. If the result is, say, , that's our empirical estimate.
The Law of Large Numbers ties them together. As the number of trials grows, the empirical proportion converges to the theoretical value, provided the model is correct:
In quant finance, both views show up daily. Black–Scholes is theoretical: it derives an option price from a model. Implied volatility is empirical: it backs the volatility number out of observed market prices. The gap between the two is where many trading edges live.