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There is talk that between 12-1 PM on Route 14 that it rains, but that's just one place and one time. Are the rain times throughout Kalos fully documented? Rain can be good (for Sligoo) or bad (for sweet scent). It would be nice to be able to plan my training based on what weather to expect.

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I think in most places it's random, I never pay attention to this stuff though .-.
Don't think so
It rains around laverre the most and in lumiose the least (if at all).
It's random I asked a similar question
It won't be random. It'll be clock based.
I think you're right Scizornician. I've just checked a dozen different times between my two games and although it is very sporadic, they always have the same weather. The rain comes and goes in 10 minute intervals. It's no wonder people think it's random. I'm convinced it's not. It may be different for each day of the week, though...

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There is no given information on when or how often it rains, but there are routes where it rains more often then elsewhere. The two routes reported to be more rainy are Route 14 and Route 8.
For other generations the time it will rain is more specific, but in Gen VI it just says "some days"

image

Don't quote me on this but I think Rain dance might be able to make it rainy, too. But if you plan on evolving Sligoo it will not work, because it needs to be natural rain.

You can also make it rain by changing the 3DS date and time, it's better explained in this video.

Source
Hope I helped.

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Although not actually documented (Bulbapedia document it as "some days"), the most common time for it to rain is on Route 14 around 12:00 pm on a Monday.
This is not guaranteed to work but has produced a lot of success for trainers trying to evolve their Sliggoo.

Sources:

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Route 14 isn't a time :P