i m using unity 4.3.1
I would guess you try to open it via windows explorer. Otherwise, you need to go to Edit->Preferences->ExternalTool->ExternalScriptEditor
MonoDevelop is the one by default but VS will show if it is on your computer or you can assign any with Browse.
Open Unity, go to: Edit → Preferences → External Tools → External Script Editor
And see if MonoDevelop is selected.