The direct oxidation of low-concentration methane (CH
4
) to methanol (CH
3
OH) is often regarded as the
“holy
grail”. However, it still is very difficult and challenging
to oxidize methane to methanol in one step. In this work, we present
a new approach to directly oxidize CH
4
to generate CH
3
OH in one step by doping non-noble metal Ni sites on bismuth
oxychloride (BiOCl) equipped with high oxygen vacancies. Thereinto,
the conversion rate of CH
3
OH can reach 39.07 μmol/(g
cat
·h) under 420 °C and flow conditions on the basis
of O
2
and H
2
O. The crystal morphology structure,
physicochemical properties, metal dispersion, and surface adsorption
capacity of Ni–BiOCl were explored, and the positive effect
on the oxygen vacancy of the catalyst was proved, thus improving the
catalytic performance. Furthermore, in situ diffuse reflectance infrared
Fourier transform spectroscopy (DRIFTS) was also performed to study
the surface adsorption and reaction process of methane to methanol
in one step. Results demonstrate that the key to keep good activity
lies in the oxygen vacancies of unsaturated Bi atoms, which can adsorb
and active CH
4
and to produce methyl groups and adsorbing
hydroxyl groups in methane oxidation process. This study broadens
the application of oxygen-deficient catalysts in the catalytic conversion
of CH
4
to CH
3
OH in one step, which provides
a new perspective on the role of oxygen vacancies in improving the
catalytic performance of methane oxidation.