The reading for this one is pretty tricky, and I'd consider it an exception. To remember it, you have to learn the 兄 part, and everything else will fall into place. Here's a mnemonic to help you:
Your (kind) older brother pushes you down on the ground. You stand up and look at your knee (にい), which is all bloody. "Why'd you do that to my knee!?" you ask. "You're supposed to be a nice older brother, that's why I call you お兄さん!"
Which one is Takashi’s older brother?
The delivery guy today had exactly the type of face I go for.
I can’t help thinking about my older brother’s nose hair.