I own mid/entry level PSB 2B's bookshelf speakers but I have heard most of their lineup. It's kind of hard to give a direct comparison because the approach to the speakers are very different. The polks use 5 drivers and a tweeter and while two speakers form PSB use the same configuration they are in the Platinum series and they start at about $5000 US so it's not a fair comparison. By the way I have heard the Platinum T8's and they are amazing. Can't say enough good things about them. Not much out there can touch them in any price range IMO. If you want to go based solely on specs then a fair comparison would be the image series t65 vs the Rti12. They would stack up well on paper. Both speakers claim 30hz as the low point, both are 3 way speakers, they are priced to within 3 or 4 hundred dollars of each other, both come with similar accessories, and both are biampable. They are very different speakers however. Also to be honest I don't trust Polks figures as much as PSB's. Take a look at the charts for both speakers and see what info is missing. Little things like the fact that PSB measures its output in an anechoic chamber, includes both shipping and unpacked weights, includes off axis measurements, etc.. There is also the fact that Polk makes this speaker look like it is pretty efficient when it is not. They say it is 8 ohms and 90db sensitive but I'd bet it spends a lot of its time around 4 ohms and < 90db efficiency from what I've heard from other RTI owners. There's nothing wrong with that at all, but they should post the minimum sensitivity, PSB does.
Ok, here where I say what I think is the better parts about each speaker. The Polk has more drivers including 2 mid bass drivers so I'd bet you get a fuller sound with clearer midbass. The Polk is heavier. The Polk is a nice big tower (IMO if you are getting a big tower get a big tower, not something that needs a stand under it). I think the Polk looks better and I like the real wood finish.
The PSB is cheaper. The PSB uses an aluminum tweeter (I like, many don't). The PSB is rated more honestly. The PSB is more efficient despite being a 6 ohm speaker. PSB is Canadian. The 65T is a second generation speaker that improves on an already fantastic speaker. I know the components inside the PSB are of very good quality (with the polk I'm only 99% sure that they are good quality). Psb is conservative when rating their speakers. UMMMM... the PSb is Canadian.
Which one do I think is better? Probably the Polk overall but I've never auditioned the speakers side by side, only heard them seperatly. That doesn't meant the Polk is better, there are many variables to consider. You will need a more expensve receiver or seperate amps to enjoy the Polks to their fullest while the same is not true of the PSB. The PSB is more of a budget buy. If you were to go to the PSB Stratus Silver i then it would be more expensive than the Polk, and while the Stratus has what I would say is a much better quality of sound the Polk would still have it beat it almost every spec. Also the Stratus are probably more power hungry than even the polks.