The invention discloses composite calcium naphthenate-based tetra-polyurea lubricating grease which is characterized by including following components, on the basis of the weight of the lubricating grease, 20-60 wt% of non-Newtonian calcium naphthenate, 1-10 wt% of a calcium salt of a higher fatty acid, 0.5-25 wt% of a polyurea compound and 25-70 wt% of a basic oil. An infrared spectrogram of the non-Newtonian calcium naphthenate has a characteristic absorption peak of aragonite-type calcium carbonate. The polyurea compound is a tetra-polyurea compound. The invention also discloses a preparation method of the composite calcium naphthenate-based tetra-polyurea lubricating grease and the composite calcium naphthenate-based tetra-polyurea lubricating grease prepared through the same. The composite calcium naphthenate-based tetra-polyurea lubricating grease has excellent anti-corrosion property and anti-salt fog property, and has performances comprising a high-temperature-resistant performance, a water-resistant performance, an adhesive performance, a colloid stability and the like, which are better than those of a composite calcium sulfonate-based tetra-polyurea lubricating grease. The composite calcium naphthenate-based tetra-polyurea lubricating grease has a longer lubricating service life.