PCSX2 does not have a native "Windowed Mode" toggle in the GUI. However, you can simulate it:
Config → Video (GS) → Plugin Settings → Internal Resolution → Set to Native (512x448) or 2x (1024x896). Uncheck "Stretch to Fit". The GS window renders at that size on your desktop.
Create a virtual desktop at lower resolution. Run PCSX2 fullscreen there. Switch desktops (Win+Tab / Ctrl+Win+Left/Right) instantly.
If dual monitor: Set PCSX2 fullscreen on Monitor 2. Keep Monitor 1 for Discord/Guide. Not windowed, but functional separation.
Some games (e.g., Final Fantasy XII, MGS3) have community patches enabling "Windowed" via pnach cheats modifying GS registers. Search PCSQ2 forums / GitHub.
Borderless Gaming + Native Res is the most stable "windowed-like" experience today.