The "electoral college" isn't some mysterious group of folks voting to elect the next pope...
Each party designates their own choices for who they want to be the electors - well connected party faithful.
Whichever party wins the popular election in a state, that party chooses the delegates who will submit the EC vote. The chance of EC voters "going rogue" is therefore vanishingly small. You're not going to have a candidate win the pop vote in a given state and have the electors go the other way...it just won't happen.
The "problem" with the EC...for those that believe there is one (I don't)...and the reason one can (conceivably..it's happened 4 times) win the national popular vote and lose the EC vote is two-fold.
First, in nearly every state, it doesn't matter if the vote comes down to 4,000,001 to 4,000,000 - a win is a win, so that person gets the same ~ 20 electoral votes as a candidate who won 8,000,001 to 0.
Second, Each state has a # of EC votes based on the number of senators and reps. The catch is every state has 2 senators, while # of reps is based on population. This means that smaller states have a slightly larger weighting in the EC system. Let's say for sake of argument the rule is 1 House rep for every million residents (I don't know what the actual # is, but I know that isn't it). A state with 2 mil residents gets 4 electoral votes (2 reps, 2 senators) - or 1 for every half million residents. A state with 40 million would then get 42 votes - 40 for the population, and 2 because every state has 2 senators...thus each EC vote here represents over 950,000 people.
Just to be clear - senators and reps aren't the actual EC delegates - the delegates are a group of party faithful equal in number to the # of sen+reps.