I have RC23 Directv Remote. I currently turn my TV and Directv Receiver
on/off with the TV power buttons. I have added a Pioneer Audio Receiver and have
programed the Pioneer Receiver to AV1. I would like to turn all three components
on/off with a single button (one button=on. different button=off) like I am able
to do with my TV and Directv receiver. Is there any way of doing this?

No. The "Master power button" is only for the Directv receiver and the TV.

Yes........by a Harmony remote........ they are the best thing ever invented.

As someone just switching to Direct.. I have to say, this is the most illogical thing. If I add an AV1 to the setup.. it should get powered on/off too.

With 3 TVs, I only have one where the Direct remote isn't cumbersome.. a powered Vizio soundbar which auto-senses its input and will turn itself off. For the other 2 sets, running thru Denon AVRs, the Direct remote qualifies its designer for 50-lashes with a "duh" noodle.