A voltmeter will at least tell you which pin is the base, since both b-e and b-c junctions are the same type. If you have a simple transistor tester, you can find out which way the transistor is operating by the asymmetry in forward and reverse beta.
The other thing you can look at with a voltmeter is the leakage current and breakdown voltage across the two junctions. Standard vertical transistors use a degenerately doped emitter, which usually means that the emitter base junction will have higher leakage as well as a lower reverse breakdown voltage. The collector-base junction is usually lightly doped on both sides, thereby resulting in lower leakage currents as well as higher breakdown voltages. TTFN