So, just to be clear, you mean rendering the characters and background separately, then putting them together in Photoshop/Another photo editor? I don't generally do this myself, but the issue that arises from rendering in layers (so to speak) is that you lose the reflection/ambient lighting created by objects around the model that aren't necessarily on camera by turning them off. The floor in the render below is putting a lot of work in brightening the rest of the scene from the lighting above, for example. That said, I don't know how those who practice this style of rendering tend to circumvent that, so someone may have a more appropriate answer in that regard. But something of a hack in this regard is spot rendering characters over a the environment.
So, I already have the lighting and general environment ready to go for this render below.
View attachment 2042457
So, in order to do what I mentioned above, you're going to turn off your figure/model, but keep the lighting and environment intact. Excuse all the noise as I'm just quickly rendering these to show you the process if it's something you'd like to use.
View attachment 2042465
So, once you have your background rendered to a point of your liking, you'll want to turn your figure back on. Now, keep your figure and lighting/environment on. Now go to "Tool Settings" (Window > Panes (Tabs) > Tool Settings if you don't see it on your screen, iirc.) > Spot Render > Select "New Window". Now you should have a camera icon when you mouse over the viewport. From here you want to left-click+hold and drag over your desired model. Make sure her entirety (within the constraints of the viewport) is within the box you drag out for the model. If you mess up, right-click (while still holding the left-click you made earlier) while in the viewport and it'll clear the selection you dragged out.
All said and done, you should have something like this:
View attachment 2042470
Now you take it into Photoshop, drag the background into Photoshop first (or on a document you've already opened at your preferred size. Just keep aspect ratios in mind. If you render at 16:9, make sure your document size is at 16:9. Same goes for 4:3 or 1:1. This allows to scale up or down as needed without cropping parts of the image off or squishing it to make it fit.
All finished, you should get something to this effect:
Every now and then, you may get a black box around a spot render. I didn't get one here, but I do get them at times. Any competent Photo editing software that offers masks (in this case a layer mask with Photoshop), should be able to get rid of them fairly quickly. That said, as I mentioned above, I'm not very knowledgeable when it comes to rendering in separate layers, so might want to wait for someone else on that.