I want a $20\%$ margin on the selling price.
In your computation $$\text{selling price}=1.2\times\text{cost price},$$ the markup percentage (profit $\div$ cost price), or percentage profit, will be $\dfrac{20}{100}=20\%.$
In your coworker's computation \begin{align}\text{selling price}&=\text{cost price}\div(1-0.2)\\&=1.25\times\text{cost price},\end{align} the profit margin (profit $\div$ selling price) will be $\dfrac{25}{125}=20\%,$ as desired.
P.S. While profit margin is the more immediately relevant metric to sellers, markup percentage is the more fundamental concept, at least to analysts and buyers.