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Divine Smite can be used when the player makes a successful melee attack and at level 11 improved divine smite automatically adds 1d8 damage to all melee attacks. When wielding the tentacle rod you use your action to direct each of 3 tentacles to attack at +9 that do 1d6 damage.

Can I use Divine Smite for all 3 of these attacks? For any of them?

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No

The rules

The main reason for this is that the Tentacle Rod makes melee attacks, while Divine Smite requires melee weapon attacks.

Melee attacks (PHB p. 195)

Used in hand-to-hand combat, a melee attack allows you to attack a foe within your reach. A melee attack typically uses a handheld weapon such as a sword, a warhammer, or an axe. A typical monster makes a melee attack when it strikes with its claws, horns, teeth, tentacles, or other body part. A few spells also involve making a melee attack.

So melee attacks are considered melee weapon attacks only when made with a handheld weapon, otherwise they are plain melee attacks (coincidentally, tentacles are actually given as an example of this case).

The difference between the different types of attacks is very well explained by Dale M in his answer to a different question, but to reiterate:

There are 2 axes of attacks: every attack is "weapon", "spell" or "one of the specifically listed things that are neither (e.g. unarmed, grapple)" and "melee" or "ranged".

Additional musings

Tentacle rod

While holding the rod, you can use an action to direct each tentacle to attack a creature you can see within 15 feet of you. Each tentacle makes a melee attack roll [...]

Given that the attack is made by the tentacle itself, while the PC uses his/her action to use (command) the rod (which isn't a function of the Use an object action - DMG p. 141) and not take the Attack action, this could also be argued that disqualifies the attacks for the Divine Smite requirement, as you have to be the one making the attacks:

Divine Smite

Starting at 2nd level, when you hit a creature with a melee weapon attack[...]

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    \$\begingroup\$ +1 for the Additional Musings section - it's a much more convincing argument than the one in your main section, especially since monster attacks are, with very few exceptions, melee or ranged weapon attacks (see the Monster Manual). \$\endgroup\$ – Miniman Apr 14 '16 at 10:19
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    \$\begingroup\$ Personally I'd toss out most of the answer and build on what you've got under "Additional Musings." It seems clear to me that when you use the Rod of Tentacles, you are not making an attack at all -- it is the rod that makes the attacks. \$\endgroup\$ – LegendaryDude Apr 14 '16 at 12:12
  • \$\begingroup\$ The first half of the answer is false. "Weapon Attack" means roughly the same thing as "Physical Attack". Unarmed Strikes, such as from the Monk, are Melee Weapon Attacks, yet your Fists are not considered a weapon. Additionally, throwing a flask is considered an Improvised Attack and a Ranged Weapon Attack, yet the flask is not considered an actual weapon. \$\endgroup\$ – Daniel Zastoupil Mar 28 at 21:45
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The tentacle rod is a weapon that makes melee attacks; the paladin's smite requires melee weapon attacks. So, yes, if you are willing to spend the spell slot you can smite on each hit..

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    \$\begingroup\$ @Olorin don't want to nitpick your nitpick but the description for the Tentacle Rod specifies "Made by the drow, this rod is a magic weapon that ends in three rubbery tentacles." \$\endgroup\$ – nicksgen Apr 14 '16 at 10:58

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