Taken from Wikipedia:
Although widely attributed to Edwin Hubble, the law was first derived from the general relativity equations by Georges Lemaître in a 1927 article where he proposed the expansion of the universe and suggested an estimated value of the rate of expansion, now called the Hubble constant.
Two years later Edwin Hubble confirmed the existence of that law and determined a more accurate value for the constant that now bears his name. Hubble inferred the recession velocity of the objects from their redshifts, many of which were earlier measured and related to velocity by Vesto Slipher in 1917.
So it was first predicted using GR by Lemaitre and then measured by Hubble. It's not Doppler effect because there's not a notion of relative velocity in General Relativity (unless the two object are close and in a region with negligible curvature ).