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I was level grinding on Route 117 and battled an Illumise with my Kangaskahn and I used Ice Punch, and missed! The only way I can explain this was the dexnav exclusive item Brightpowder, but I was on my bike. My understanding is you can't encounter dexnav spots if you're on the bike, you'll scare them away before you get there. Can any one explain this? Have I just exposed these exclusive items as very much NOT exclusive? Is it possible to ride up fast on a dexnav spot without scaring the Pokemon?

That's strange... none of its abilities raise evasion, it doesn't learn any evasion raising moves through level up or egg moves... the only possibility is the bright powder.
I think I'm onto something, I have a Persian with Switcheroo, so I used it and I just got a potion from a Zigzagoon. Again, without using DexNav. Can some one please test this so I know I don't have a glitched game
The Zigzagoon likely had Pick-up, and had "picked up" a Potion.  It's the route from Mauwville to Verdenturf with the Daycare, right?  That's before they are high enough level start getting Super Potions regularly.  I have straight caught a number of Zigzagoon holding Potions without the DexNav.

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The Illumise must have held a Bright Powder. It has a 5℅ chance of finding one in the wild randomly.

Hope I helped!

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Thanks. The problem now is this just creates more questions. Serebii has these items listed as 'DexNav exclusive'. The only thing 'exclusive' about these items is that they are exclusive to oRaS. It seems that Serebii has been misinformed (if you're reading this Serebii, may I suggest a modification to your site to reflect this new information). So this leads me to another question: http://pokemondb.net/pokebase/262159/can-pokemon-with-oras-exclusive-items-have-their-item-in-oras