One possibility would be to take the logarithm:
$$ \ln(0.95^{32}) = 32 \cdot \ln(1-0.05) \approx -1.6 $$
because $\ln(1+x)\approx x$ when $x$ is small.
Perhaps the colleague has memorized the natural logarithms of a handful of small integers. In particular, $\ln 5=1.609...$ (you can remember that because an English/American mile is very nearly $\ln 5$ kilometers; or perhaps because $\ln 5\approx \phi$, the golden ratio which involves $\sqrt 5$ and appears in pentagrams), so $e^{-1.6}$ is about $1/5$.
Alternatively, with common (base-10) logarithms:
$\log(1+x) \approx \frac{10}{23} x $ (one needs to memorize this conversion factor), so $$\log(0.95^{32})\approx -\frac{10}{23} \cdot\frac{1}{20} \cdot 32 = -\frac{16}{23} = -1+\frac{7}{23}$$
But $3\cdot 23=69$ so $\frac7{23}\approx 0.3 \approx \log 2$ (another remembered value). Again, the result must be close to $0.2$.