You can write your own function that accepts a string and converts it to a Date using the format you want, then use the setAs to set it as an as method. Then you can use your function as part of the colClasses.

Try:

setAs("character","myDate", function(from) as.Date(from, format="%d/%m/%Y") )

tmp <- c("1, 15/08/2008", "2, 23/05/2010")
con <- textConnection(tmp)

tmp2 <- read.csv(con, colClasses=c('numeric','myDate'), header=FALSE)
str(tmp2)

Then modify if needed to work for your data.

Edit ---

You might want to run setClass('myDate') first to avoid the warning (you can ignore the warning, but it can get annoying if you do this a lot and this is a simple call that gets rid of it).