1.01 - Pilot

Chloe and Clark stop by the Talon to get coffee and talk about where he might go to college (we already know that Chloe is going back to her home town of Metropolis togo to Met U in thefall.). Clark talks about going to Miami (he checked it out in Run with Bart, and it's a set up for Aqua.) While they are there, her cousin on duty is robbed and doesn't remember it. Clark rushes outside to confront the robber who zaps Clark - erasing all his memories (and we see a still from every episode in the series thus far.) Chloe comes running out of the Talon to check on him, and Clark looks up at her confused. "Clark who?"

Chloe is crusading against the Prom Queen tradition at SHS; she sees prom as the senior class's last party together and sees it needless to cap off four years with a popularity contest.  Lana notes that "Chloe Sullivan strikes again" but also remarks "balloons and taffeta seem a little harmless compared to your usual targets."  Chloe tries to twist Lana's arm to going stag even if it's just to hear Lifehouse when they get cornered by Dawn Styles who warns Chloe to back off.  Chloe is shocked and appalled to find she was nominated for Prom Queen.

The story starts off with Chloe putting a bet on the football game to Mikhail Mxyzptlk* - a foreign exchange student who has the power to control the odds.  Chloe puts her money down on Smallville to win, citing that she "never bets against Clark Kent" even though she hates to admit it.  Mikhail uses his powers to make Clark trip on the field and almost loose the game - he does make Clark tackle and nearly take out an opposing team member; it brings up the issue of steroids and questioning Clark's ability to play with other people.

Smallville, Episode 4.05: Chloe, Clark, and Bart

Clark ends up tracking down Bart, a kid with a handful of other Flash alias, whom stole his father's wallet.  Clark talks to Chloe and has her track down Jonathan's credit card, and with her help he finds out that the kid used it to buy a hotel room. 

Once the Pilot skips past the 1989 meteorite set up, to the present, Chloe on the bus is the very first person we see. She's not addressed by her name to her face in this episode at all; her name is said once, right before Clark gets beat up. It's not until midway through the second episode we get to match a name to the face. For the Pilot we only know her as the plucky blonde reporter who has her eyes on the real stories of the town - and on Clark.

Smallville, Episode 1.01: Chloe, Clark, and Pete

In the first exposition dialog about her character, Pete explains that Chloe is known for her obsession with the weird and bizarre in Smallville; a fact that Chloe doesn't dispute as much as she disputes her attraction to Clark. Chloe noticed Clark tapping the bus (but doesn't realize it was him) and gives us the impression that Chloe looks at Smallville through an outsiders' eyes. She also reveals that she already knows more about Clark Kent than his best friend Pete does when she accurately predicts how long it takes before Lana Lange (or more accurately, her kryptonite necklace) trips him up.
Smallville, Episode 1.01: Chloe, Clark, and Pete