Sure, moststatesgowithmajoritytakesallbut a statecoulddecidethatduetoperceivevoterfraudorinanattempttotakeadvantageofdelaysinthevotecountandsotheycouldmovetoappointtheirownelectors.
Becauseslaveryhad a hugeimpactontheformationoftheElectoralCollege, mostvoterswhitelandowningmaleslivedinthenorthbecauseSouthernstatesspotforthe 3/5 compromiseinwhichtheapportionmentforeachdatewasthestate's population, plus 3/5 ofitsenslavedpopulation.
Thenagain, in 18 88 BenjaminHarrisonnarrowlycarriedswingstatestowinthemajorityofelectors, eventhoughhisDemocraticrival, GroverCleveland, won a higherpercentageofthepopularvote.
There's theNationalPopularVoteInitiative, whoseobjectiveistogetstatestosignonto a compactthatwouldeffectivelyabolishtheElectoralCollegewithout a constitutionalamendment.