Not much difference in the result for external commands. Running env just involves an additional exec to do the variable assignment parsing which the shell would otherwise do. env -i would be more useful, since it clears the environment, which isn't that straightforward to do in the shell.
In both cases, expansions like command substitutions VAR=$(somecmd) run by the shell before the assignments happen, and both cases follow PATH etc. The only difference I can come up with is with the value of the _, which Bash sets to the name of the command it runs (but env doesn't). Of course, without env, you might also run the shell's builtin version of the command.