In some situation, you want your Raspberry HTPC to connect to an enterprise/education wifi network (with both username and password). But you cannot connect it via LibreELEC's GUI; in this case:
First, ssh into your Raspberry HTPC
After the login process, execute
cd /storage/.cache/connman
nano examplename.config
Revise accordingly (ignore the descriptive text after # ); then paste into the terminal window (try doing a right click on terminal after copying)
CACertFile=/etc/ssl/certs/certificate.cer #you might not need this line
Phase2=MSCHAPV2 #your username #you might not need this line
Passphrase=password #your password
Press ctrl+x to exit, y to confirm, enter to save the file and reboot the machine.
From the Arch Linux wiki's advisory:
Options are case-sensitive.
Consult the company/institution hosting the wifi network for various settings such as username, password, EAP, Phase2output, and certificates.
This tutorial is adapted from: