Put your multimeter on diode test, then check between all pins until you find a diode junction of about 1.2v. That is the LED.
Connect 5v to the LED through a 1k resistor, and check again that the LED is fixed at about 1.2v.
The remaining 2 pins are the opto device. Connect 5v through a 47k resistor to one pin, the other pin to ground. If you have these pins the right way around one pin will read 0v, the other about 0.5v or so.
When you disconnect the power to the LED pin the 0.5v pin will change from 0.5v to 5v.