Yes, the question is when and how.
You can enter it in the bootloader as a prerequisite to boot anything. You can also enter it at the display manager / login screen, which is a little further down the boot process.
My desktop for example can boot up to the login screen and perform its NAS and routing duties all on its own. But my user and all of my user's data is still locked at that point: the computer is usable by guests and everything but even if you manage to throw a root exploit at it, my data is completely safe. Only when I log in, either locally or remotely, my password will go through PAM which will run a script that uses my password to unlock my home directory and mount it as I'm logging in.
What changes is what is covered by the encryption, and when the key is required. My root is auto unlocked via TPM, my home is unlocked on demand as I log in to my user account.
OP's problem is they have full disk encryption so they need the password to boot up Linux at all, but they also get a second password prompt to log in when it reaches the display manager, even if it's the same password. The solution is either they configure it to auto login since you need a password for the whole OS anyway, or they automate the unlocking of the root partition and use their login password to further decrypt the home directory (or rely entirely on the system being secure that the user isn't encrypted further and it's just a password prompt, which is what I think Windows does).