Personally I would leave out the spaces and add the space when you write to the document variable e.g.
Code:
Private Sub UserForm_Initialize()
Dim myPrefixes() As String
Dim strPrefix As String
Dim i As Integer
myPrefixes = Split("[Select Item]|Mr.|Ms.|Det.|Dr.|Atty.|Rabbi|Ofc.|Sgt.|Cpl.|Maj.", "|")
With Prefix1
.List = myPrefixes
On Error Resume Next 'the variable is missing from the document
For i = 0 To .ListCount - 1
If RTrim(ActiveDocument.Variables("Prefix")) = .List(i) Then
.ListIndex = i
Exit For
End If
Next i
End With
End Sub
Private Sub CommandButton1_Click()
If Prefix1.ListIndex <= 0 Then
MsgBox "Select the prefix"
Prefix1.SetFocus
Exit Sub
End If
ActiveDocument.Variables("Prefix") = Prefix1.value & Chr(32)
Unload Me
End Sub