[vvillyd]

Absolutely! Yes!

First, NEVER work anything hot. There is no such thing as a safe voltage to work energized. Even a simple home receptacle circuit can easily kill you (and it happens with alarming regularity).

That said, ALWAYS work something AS IF it were hot (for the exact reason you said, accidents happen). This means connecting the safety measures first. The safest order to connect wires is: ground, neutral, hot. The safest order to disconnect wires is the opposite: hot, neutral, ground.