I'd recommend defining Regular and Overtime as functions that return the computed values, i.e:
Private Sub Button1_Click(ByVal sender As System.Object, _
ByVal e As System.EventArgs) Handles Button1.Click
Dim hours As Double
Dim rate As Double
Dim regpay As Double
Dim overpay As Double
hours = TextBox5.Text
rate = TextBox4.Text
If hours > 40 Then
regpay = Regular(40, rate)
overpay = Overtime(hours - 40, rate)
Else
regpay = Regular(hours, rate)
End If
Dim netPay = regPay + overPay
' TODO: write netPay back to the form
End Sub
Function Regular(hours As Double, rate As Double) As Double
Return hours * rate
End Function
Function Overtime(hours As Double, rate As Double) As Double
Return hours * rate ' Note overtime may be paid at a different rate
End Function
Also for accuracy in financial calculations I'd recommend using the decimal type over double.