Madrid/ Barcelona Itinerary suggestions

It's doable but pretty busy. If Oct 24 is your arrival day in Madrid (jetlagged after an overnight flight?) and Nov 2 your departure day from Barcelona, you have ten full or partial days, and it looks like you'll be on trains during four of them. If two days in Valencia means two full days, then 40% of your days will be spent getting there, being there, and getting back to wherever's next. Is Valencia worth that time investment? Without Valencia, you'd have a much easier trip, with two big cities and an easy Toledo day trip.

A "day trip" "along the way to Barcelona" presumably means a multi-hour stopover somewhere. I haven't been to Zaragoza (except through it on the train) but other posters have recommended it. You'll need to see whether there's a way to store your luggage at or near the station.

Please clarify your fight dates. Do you arrive in Spain on Oct 24 or Oct 25? Is Nov 2 the day you fly home? It looks to me as if you have as few as seven full days in Spain, which would be quite tight for Madrid, a side trip to Toledo and Barcelona.

Barcelona and Madrid have more sights than Valencia, and including Valencia in your itinerary will cut into the time needed for the other cities. In addition, you'll incur extra travel time:

Madrid-Barcelona......2:30

Madrid-Valencia..........1:49
Valencia-Barcelona...3:08
Total............................. 4:57 (Double the travel time)

I forgot to mention were arriving on the 24th at 8 a.m. and leaving on the 2nd at 10 p.m. Thanks!

OK, so 8 full days plus--maybe--some hours on the arrival day if your body handles the overnight flight well. That doesn't seem long enough for the diversion to Valencia to me. But maybe you have a pretty clear list of sights you want to see in Madrid and Barcelona and are confident you can knock them off (and include the day trip to Toledo) in six days? Madrid and Barcelona are a lot larger than Valencia, and you'll lose half a day moving from Madrid to Barcelona even if you're very efficient..

If it were me, I would eliminate Valencia from your itinerary. Otherwise, your trip is very rushed. Both Madrid and Barcelona are large cities with many interesting sites. And a trip is more rewarding if you make time for wandering through neighborhoods, exploring, and coming upon the unexpected. You will need time to get over jetlag in Madrid, too. You have 9 nights on the ground. This is what I suggest for a more enjoyable trip and less rushing around:

Madrid - 5 nights to include a daytrip to Toledo (remember that 5 nights gives you 4 full days).
Barcelona - 4 nights

OR you could spend 4 nights in Madrid (including the daytrip to Toledo) if you aren't that interested in art museums. Madrid has some outstanding art museums so it depends on how many you want to visit.
And spend 5 nights in Barcelona to see the Gaudi sites, other interesting sites, the cathedrals, explore interesting neighborhoods.
And remember to book some of the Gaudi sites in advance.

If this is your first time to Spain - and it sounds like it is - I would skip Valencia this time.

Rather, I would use the time you would have allocated to Valencia to spend more in Madrid and Barcelona. Choose where you want to spend more time based on which city interests you most; you can’t miss no matter which you choose as both cities are amazing.

If you decide to side trip, I would do Toledo if you plan to spend more time in Madrid and Monserrat if you choose more time in Barcelona. Just my preferences. Others may have different thoughts.

Enjoy some pastries at La Mallorquina in Puerta del Sol (Madrid) for me. It’ll be very busy but it’s worth it!