Not exactly. What you want to avoid is using biggest-biggest or smallest-smallest (physical size that is). What you are looking to avoid doing is making your chain go diagonal.
It gets a big confusing because your biggest rings on the back are the easiest gears, but on the front your smallest ring(s) are your easiest. The biggest rings are closest to your hub on the back (inside) - smallest rings are on the outside. On the front your big ring is on the outside, small ring(s) inside. So trying to use the extreme ends together makes your chain stretch diagonally. It will usually rub against the derailleur and it tends to wear your rings and chain faster.
Hopefully I don't have you terribly confused now....




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