The grain is the direction of the muscle fibres. Against the grain means to cut across the fibres.
For tougher cuts of meat (and meat generally) or cuts with long grains (eg london broil), cutting across the fibres makes it easier to chew and the meat feels more tender. If you cut along the grain, the muscle fibres remain long and it makes the meat feel more tough and chewy – most people find this less nice to eat.
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