The reasons for the difference of visible light activity between the direct contact g-C3N4/TiO2 Z-scheme composites obtained by one-step or two-step calcination process were investigated in detail by XRD, TEM, XPS, Raman and ESR technologies. TEM results showed that only g-C3N4 obtained by two-step calcination (denoted as CN-TSC) presented the porous structure which was in favor of the light absorption. XPS analysis indicated that interstitial doped N species formed in one-step calcination composite (denoted as CT-OSC) while substitutional N would appear in two-step calcination composite (denoted as CT-TSC). Nevertheless, interstitial N located at the higher position in the band gap of TiO2 and usually acted as the strong capture center of holes which was unfavorable to charge transfer. ESR and Raman results indicated that CT-TSC with some concentration of surface V-o center dot and lower concentration of bulk V-o center dot had excellent charge separation efficiency, according to the surface-enhanced Raman scattering (SERS) results of photo-induced charge-transfer (PICT) enhancement mechanism. And as a result, the visible-light activity for propylene oxidation of CT-TSC was twice higher than that of CT-OSC.