A series of 4-phenylpiperidinyl and 4-phenylpiperazinyl alkyl spaced 5,5-diphenylhydantoins was prepared and evaluated for affinity at σ sites. Increasing the alkyl spacer between the two pharmacophore recognition units resulted in a progressive increase in σ binding affinity. The pentyl 12 and hexyl 13 4-phenylpiperidine derivatives exhibited subnanomolar affinity (0.7 nM and 0.6 nM) for the PENT site.