Interesting skill uses I can recall from my 4e game:
*Using Athletics to jump over a hyena pack which was blocking the 10' wide corridor, in order to relieve the pressure on the paladin who had become isolated on the other side of the swarm.
*Using Arcana to "minionize" an isolated NPC, so that he could then be killed with a single magic missile.
*When a temple was collapsing due to the destructive magical forces of a thwarted ritual, using Arcana to control the extent of the collapse, so that the whole mountainside didn't go down with the temple.
*Using Arcana, in combination with a statue of the Summer Queen, to dispel a black dragon's darkness aura.
*Using Arcana, when casting area fire spells while fighting in a library, to stop the scrolls and books from catching on fire.
*Many amusing Bluffs to create a diversion to hide, from the Sorcerer-multiclass-Cuthroat (not especially creative, but the player generally manages to get a laugh).
*Using Intimidate to hold off a wolf-riding goblin long enough for weaker allies to run to safety behind a pallisade.
*Using Religion to seek guidance, to purify statues dedicated to evil gods/demons, and to curse a wight in combat so as to gain combat advantage against it (not all this is especially creative, but it creates a nice opportunity to inflict psychical backlash if the skill roll fails).
*Using Stealth and Thievery to cache some items in a hidey-hole when having travelled back in time, so that they could be extracted from the hidey-hole once the PC returned to the present.