It depends on what you want to change: is it the size of the buttons or the size of the icons ?
To change the size of the buttons, use SetToolBitmapSize (24x24 for instance):
toolbar.SetToolBitmapSize((24, 24))
This will only change the size of the buttons, though. If you want to change the size of the icons, simply use bigger ones. The easiest way is to use wx.ArtProvider:
wx.ArtProvider.GetBitmap(wx.ART_FILE_SAVE, wx.ART_TOOLBAR, (24, 24))
So, summing it up:
# Define the size of the icons and buttons
iconSize = (24, 24)
# Set the size of the buttons
toolbar.SetToolBitmapSize(iconSize)
# Add some button
saveIcon = wx.ArtProvider.GetBitmap(wx.ART_FILE_SAVE, wx.ART_TOOLBAR, iconSize)
toolBar.AddSimpleTool(1, saveIcon, "Save", "Save current file")
Remark: As SetToolBitmapSize changes the size of the buttons, not the size of the icons, you can set the buttons to be larger than the icons. This should leave blank space around the icons.