Quite the opposite. In states with large populations, more voters compete for fewer electoral votes.
Census Data
California
Population: 33,871,648
Electoral Votes: 55
Citizens per Electoral Vote: 615,848
Arkansas
Population: 2,679,733
Electoral Votes: 6
Citizens per Electoral Vote: 446,622
Wyoming
Population: 493,782
Electoral Votes: 3
Citizens per Electoral Vote: 164,594 (!)