InP nanowires were grown on 111B InP substrates by metal-organic chemical vapour deposition in the presence of colloidal gold particles as catalysts. Transmission electron microscopy and photoluminescence measurements were carried out to investigate the effects of V/III ratio and nanowire diameter on structural and optical properties. Results show that InP nanowires grow preferably in the wurtzite crystal structure than the zinc blende crystal structure with increasing V/III ratio or decreasing diameter. Additionally, time-resolved photoluminescence (TRPL) studies have revealed that wurtzite nanowires show longer recombination lifetimes of approximately 2500 ps with notably higher quantum efficiencies.