Plasmonic coupling of metallic nanostructures with two-dimensional molybdenum disulfide (MoS2) atomic layers is an important topic because it provides a pathway to manipulate the optoelectronic properties and to overcome the limited optical cross-section of the materials. Plasmonic enhanced light-matter interaction of a MoS2 layer is known to be mainly governed by optical field enhancement and the Purcell effect, while the discrimination of the contribution from each mechanism to the plasmonic enhancement is challenging. Here, we investigate photoluminescence (PL) enhancement from few-layer MoS2 transferred on Au nanostructure arrays with controlled localized surface plasmon resonance (LSPR) spectral positions that were detuned from the excitation wavelengths. Two distinctive regimes in LSPR mode-dependent PL enhancement were revealed showing a maximum enhancement (∼40-fold) with zero detuning and a modest enhancement (∼10-fold) with the red-shift detuned LSPR from the excitation wavelength, which were attributed to LSPR-induced optical field enhancement and the Purcell effect, respectively. By applying the experimental parameters into the Purcell effect formalism, an effective mode volume of ∼0.016λ03 was estimated. Our work provides an insight into how to utilize few-layer MoS2 as a base material for optoelectronics by harnessing Purcell-enhanced optical responsivity.