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Reading the description of the Helm of Opposite Alignment, I don't see anything which would prevent it from working on demons.

But somehow I have the strong impression that the evil of a demon is an inherent thing and unchangeable. I would be really surprised if this item did work normally on a demon.

What is the truth? Is there a rule I've overlooked which prevents it from working (or makes it much more difficult) when placed on a demon's head?

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As far as my knowledge goes, yes, a helm of opposite alignment can affect Demons.

As far as Demons&Devils go, they're "just" outsiders born on evil-aligned planes who're generally always evil and have the Evil subtype (see below) forced upon them. There is nothing mechanically preventing a demon or devil from having nonevil alignments (though they'd also count as evil on top of their actual alignment for spells that deal with alignment). They're still sentient and intelligent beings whose personalities can be changed (through experiences or force).

A subtype usually applied only to outsiders native to the evil-aligned Outer Planes. Evil outsiders are also called fiends. Most creatures that have this subtype also have evil alignments; however, if their alignments change, they still retain the subtype. Any effect that depends on alignment affects a creature with this subtype as if the creature has an evil alignment, no matter what its alignment actually is. The creature also suffers effects according to its actual alignment. A creature with the evil subtype overcomes damage reduction as if its natural weapons and any weapons it wields were evil-aligned (see Damage Reduction, above).

Considering their circumstances of creation, their experiences during life and their society and their tendency to trade souls as currency or eat them, it's unlikely for them to change alignments unless major plot (or supernatural interference like the helm of opposite alignment) happens.

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    \$\begingroup\$ A demon which turned lawful good might actually be a very interesting character. Although I think that the conflict between its chaotic evil nature and its now lawful good psychology ("killing mortals is wrong... but their souls are so tasty!") might drive it insane (insaner?) sooner or later. \$\endgroup\$ – Philipp Jun 7 '15 at 21:50
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    \$\begingroup\$ @Philipp I think it would be a highly interesting plot about a lawful good cleric trying to work with an alignment changed daemon, while continously tries to avoid her suicide. \$\endgroup\$ – Gray Sheep Jun 7 '15 at 21:54
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    \$\begingroup\$ @Phillip Well, it could be a good "suffering from inner demons" (or rather, outer demons) character spending the rest of his life searching for redemption or fighting insanity. There are many good stories with "I want to be good despite my heritage/physical form/instinctive desire for evil" type characters. \$\endgroup\$ – Shoat Jun 7 '15 at 21:59
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    \$\begingroup\$ @MorningStar, not a demon, and not quite lawful good (more neutral good), but Erevis Cale is a cleric/thief (and more to avoid spoilers) in service of an evil god fighting him on as much as possible to still do good. Read the Twilight Falling trilogy by Paul S Kemp, it's really good! \$\endgroup\$ – Blindy Jun 7 '15 at 22:43
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    \$\begingroup\$ @Philipp Succubi paladins, complete with LG alignment, is actually something of a minor trope, plus the relatively-famous Falls-from-Grace in Planescape: Torment was an LN succubus. \$\endgroup\$ – KRyan Jun 7 '15 at 23:49

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