Podés hacerlo usando la API ShellExecute. Por ej:
'en un módulo
Declare Function ShellExecute Lib "shell32.dll" Alias "ShellExecuteA" (ByVal hwnd As Long, ByVal lpOperation As String, ByVal lpFile As String, ByVal lpParameters As String, ByVal lpDirectory As String, ByVal nShowCmd As Long) As Long
'en un form
Private Sub cmdMostrar_Click()
Dim ret As Long
ret = ShellExecute(Me.hwnd, "open", "C:\docu.pdf", 0, vbNullString, 1)
End Sub
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