Yellow means "caution" because it's almost as easy to see as red
From the earliest days of motoring up until the mid-1900s, not all stop signs were red -- many were yellow, along with yield signs, because at night it was all but impossible to see a red stop sign in a poorly lit area. The yellow stop-sign craze began in Detroit in 1915, a city that five years later installed its first electric traffic signal, which happened to include the very first amber traffic light, at the corner of Michigan and Woodward Aves.
But what of those weird yellow stop signs, you ask? As materials and technologies evolved, the ability to produce highly reflective signs meant that red could resume its natural spot in the sign hierarchy, leaving the still-highly-visible yellow (it's second only to red in terms of visible wavelength) to the domain of "caution." That's why school zones and buses, crosswalks, and other important warnings are yellow today.
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