证明:$\because$ 四边形$ABCD$是正方形,
$\therefore ∠ DCB=90°,$$BC=DC.$
$\because$ 线段$CE$绕点$C$逆时针旋转$90°$得到线段$CE',$
$\therefore ∠ ECE'=90°,$$CE'=CE,$
$\therefore ∠ ECE' = ∠ DCB,$
$\therefore ∠ ECE' - ∠ BCE = ∠ DCB - ∠ BCE,$即$∠ BCE'=∠ DCE.$
在$△ BCE'$和$△ DCE$中,
$\begin{cases}BC=DC, \\∠ BCE'=∠ DCE, \\CE'=CE,\end{cases}$
$\therefore △ BCE'≌△ DCE(\mathrm{SAS}),$
$\therefore ∠ CE'B = ∠ CED = 90°.$
$\because ∠ DEF = ∠ CED + ∠ CEF = 180°,$
$\therefore ∠ CEF=90°,$
$\therefore$ 四边形$CEFE'$是矩形.
又$\because CE=CE',$
$\therefore$ 四边形$CEFE'$是正方形.