When f's upper hook meets i's dot, they collide or overlap awkwardly. A ligature redraws the two as one glyph so they connect cleanly. Metal type foundries once cast dedicated fi, fl, ffi, ffl sorts — it was standard practice, not an afterthought.
In CSS, `font-variant-ligatures: common-ligatures` is actually the default in most browsers. It only shows visibly if the font ships that ligature glyph — a system serif like Georgia may or may not, depending on OS and version. For a dedicated body-text webfont, check its actual OpenType ligature support rather than assuming.
Some code fonts also draw "programming ligatures" that merge `!=` or `=>` into a single symbol — a cosmetic aid to scanning, not a real letter-collision fix.
When to use
Leave the default (on) alone. Turn it off only when you need exact manual control over letterforms, like in a logotype.