There are few exeptions to what you can wear western boots with. Western boots can be worn with jeans or, surprise, a suit.
The jeans can be western, or casual as long as the jeans are put together with a western shirt. Only casual jeans such as Levi’s will do: those hip-hop waders will look odd, to say the least. Jean skirts are okay with boots, just be careful with the length of the skirt 
If you wear western boots with a suit, you should either be wearing a western suit, or be wearing a western hat. Remember that jean shirts do not go with suits, western or otherwise. You might find that western boots do not go with most dresses but will go with all western dresses, and western skirt outfits.
Denim dresses go well with western boots, and a western hat but if you work in an office it is only good for casual Friday, Stampede Week, Buffalo Days, or Klondike Days…etc.
Western blazers are fine with jeans and western boots. You can add hat, and a big western buckle into the mix too but not too big of buckle though, as there are comfort issues at work. A denim shirt would be okay as long as it is a different colour than your jeans. With this outfit, ties are unnecessary. A bolo is fine, as are collar tips. 
Normal T-shirts don’t go very well with western boots, but they can if they have a western image like a cactus, a horse, a cow, country singer, or an advertising with a western theme (like Rocking Horse Saloon) or a western wear brandname (like wrangler) worn with a western hat.
A western shirt like this is naked without the combination of western jeans, boots, and hat.

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