The patch is around 99% effective (when used correctly) but, as carifairy said, nothing is 100% effective at preventing pregnancy and ther is always a chance.
It works in exactly the same way as the pill (releasing estrogen and progestogen into the blood stream except it's through the skin and then stopping ovulation, thickening cervical mucas and thinning the lining of the womb).
I've never used the patch (i cannot use birth conrtol with estrogen) but I have gotten pregnant whilst using the mini-pill perfectly so it's always possible.
If you're not comfortable with the patch have you thought about non user reliable methods (implant/injection/ius/iud)? Whilst there's still a small chance of pregnancy on these they do not require you to do anything and are the most reliable forms.