Most of the people who say they pay cash for weekends, do not stay at a
DVC resort for the Friday and/or Saturday nights. They book something off site (and perhaps visit other Orlando attractions during that time) or they stay in one of the other Disney hotels.
We never pay cash - bought enough points to stay for an entire week during the season(s) we prefer to travel. Personally, I hate to change resorts - to me, changing resorts takes away my valuable vacation time!
You can pay cash (via CRO) for weekend nights at a DVC resort, subject to availability. Sometimes, MS will have availability for you to pay cash. If so, you can get a DVC Member 25% cash discount. These 25% discounted rooms come out of the DVC room inventory, not the CRO inventory. Lately, availabilty for MS cash discounts has been very limited.
So yes, you can call and try to book the weekend on cash - either by calling CRO (like any other member of the general public) or by calling MS for a 25% DVC Member cash discount. Again, keep in mind that everything is subject to availability.
If you do get a Member's discount or decide to book the weekend via CRO, be sure to ask that the reservations be linked - that way you will not have to move (change rooms).
Please try not to worry about asking questions. We all love to help and all of us were new here once. I've been reading this board for more than two years and I still have questions. So ask away!
Enjoy your trip!