Yes, once you have them added to the main repeater Hubitat can talk to them. However, you need to know their "integration id" number. Ordinarily you get this from the Essentials software. There is another method to find the number:
Connect to the main repeater with a telnet session from a terminal app on you PC. Credentials are username: lutron, password: integration. Then hit a button on one of your Picos or other devices. For a Pico you will see a message on telnet that looks like
~DEVICE,12,2,3
The 12 in that example is the integration id. The 2 is which button was pushed, and 3 means pushed.
Other devices may look like this:
~OUTPUT,5,1,100
In that one, the 5 is the integration id. This was a switch turned on.
Then you can setup the Lutron Integration app, giving the devices names, identifying them with the integration id, and selecting what type of device it is. This creates virtual devices in the Hubitat system that correspond to the Lutron devices, and behave accordingly.