Yes, there are a few methods: truth tables, axiomatic (or "Hilbert-style") systems, natural deduction, and others. The method of truth tables is probably the easiest to prove complete and correct, and it runs in exponential time at worst (the problem is actually co-NP complete).
I'm not sure what your additional question asks. Any formal system for propositional logic has only finitely many axioms or axiom schemas (e.g. "$(A\to(B\to A))$ is an axiom, for any well-formed formulas $A, B$") and finitely many deduction rules. It's usually clear that the axioms/axiom schemas/starting set of truths are tautologies, and for formulas of human-friendly lengths, we can usually see whether they're instances. But tautologies can be arbitrarily long. Given notations currently in use, for formulas longer than some threshold (say, $10^{10}$ symbols), there's no way anyone can see if a formula is a tautology just by looking at it.