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12 O'Clock High began in 1964 and was in B/W the first two seasons before switching to color in the abbreviated third and last season. Also Danger Man could technically make the list, as the last two episodes -filmed in 1967 for the aborted fourth season- were in color.

I understand that the first episode of Laramie was filmed in color. At least I've seen color scenes from it. Also the pilot for Lancer was in black and white and later the whole series (1968-70) was in color, of course. The official first episode is a remake of the pilot, shot in color.