Oftentimes they don’t. Incidents of an army accidentally attacking its own units (sometimes called *friendly fire* incidents, because you’re firing at people you’re supposed to be friendly toward) constitute a major problem in war, and modern technologies have arguably made it worse.
This has led to many standards of identification over the years. Ancient armies used standards: banners or statues attached to long poles, so that a soldier could know where to find friendly units. Uniforms and camouflage patterns evolved along similar lines. Knights’ coats of arms actually served a similar purpose, since you can’t really tell what a person in full armor looks like. Knights would wear these emblems on their shields or other conspicuous places, partly so that friendly forces would not attack them.
In more recent years, radio beacons called IFF (Identify Friend or Foe) systems are often used, so that units can be sorted out from far away. That’s important for long-range missiles, artillery, or drone attacks, where the operator generally can’t see the target and has to rely on other forms of identification. But the beacons fail sometimes, and when they do, friendly fire incidents can happen.
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