Daredevil has had a plethora of trying times in his life, but one of the most significant has to be the time Bullseye introduced Elektra to the pointy end of one of her Sais as written and illustrated by Frank Miller and Klaus Janson in Daredevil #181.
Not only was the death of Elektra surprising to the readers, but it also helped to define Daredevil from that point forward, and proved to the comics community that even popular characters could be killed... even if it's only a temporary death.