The one that gave me pause - for the first time - was Jules Bastien-Lange's "October" (1878). It's closer to my usual tastes than most else of what was in the room, particularly the way the fields and horizon in the background are done.
The ones that are most quintessentially part of the NGV for me - and I know for many others - are all large format and all, to me, suspiciously allegorical, sentimental or both. But they have a directness and a force that makes them memorable.
August Friedrich Albrecht Schenck - "Anguish" (c. 1878)
Lucy Kemp-Welch - "Horses bathing in the sea" (1900)
Briton Riviere - "A Roman holiday" (1881)
St George Hare - "The victory of faith" (c1890-1891)
Jules Lefebvre - "The grasshopper" (1872)
And three other discoveries from this latest visit - probably I've seen them all before but they've never registered:
William Quiller Orchardson - "The first cloud" (1887) - not sure what's going on here but I like the expression the man's face and the staging of the scene in general
Walter Sickert - "The Rise of Lazarus" (1928-29)
Keeley Halswelle - "Green-robed senators" (c. 1880)