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For the Duet, the ESP is hooked up with SPI with different firmware, not Serial: https://github.com/Duet3D/RepRapFirmware/blob/dev/src/Networking/ESP8266WiFi/WiFiInterface.cpp#L399
So it's better than Serial for sure. It's why the SKR Pro, which did have the esp8266 port, but was only wired for serial, required more pins for RRF: https://github.com/gloomyandy/RepRapFirmware/wiki/SKR-Pro-Wifi
I definitely prefer Klipper over RRF too. But if you know Klipper, you should know Mailsail or Fluidd over Octoprint. There's a port of Duet's web interface for Klipper too: https://github.com/Stephan3/dwc2-for-klipper-socket